西班牙专利ES2642114A1 Complexes of iridium (III) of formula general [ir (c ^ n) 2 (n ^ o)] or [ir (c ^ n) 2 (n ^ n '&#

专利PDF首页>>西班牙专利

专利附录

专利说明

权利要求

类似技术

同族专利

引用文献

法律状态

优先权

专利摘要:
The present invention describes a complex of Ir (III) of general formula [Ir (C ^ N)2 (N ^ O)] or [Ir (C ^ N)2 (N ^ N')] A, where A is an anion, each (C ^ N) is an independent cyclometalated ligand and (N ^ O) or (N ^ N') is an arylazole ligand. The great diversity of ligands comprising these complexes are capable of modulating the energy of the luminescence in a very wide range, covering a large part of the visible spectrum. (Machine-translation by Google Translate, not legally binding)
公开号:ES2642114A1
申请号:ES201630610
申请日:2016-05-11
公开日:2017-11-15
发明作者:Gustavo ESPINO ORDÓÑEZ；Arancha CARBAYO MARTÍN；Marta MARTÍNEZ ALONSO；Larry Danilo AGUIRRE MÉNDEZ；Leticia BERLANGA SANZ；Natalia GALERÓN RODRÍGUEZ；Jairo FIDALGO ZORRILLA；Félix Ángel JALÓN SOTÉS；Blanca Rosa MANZANO MANRIQUE；Mª del Carmen CARRIÓN NUÑEZ DE ARENAS；Begoña GARCÍA RUIZ；Javier TORRES HERNÁNDEZ
申请人:Universidad de Castilla La Mancha；Universidad de Burgos；
IPC主号:

专利说明:

IRIDIO COMPLEXES (III) OF GENERAL FORMULA [lr (CAN), (NAO)) or [lr (CAN), (NAN ')] A
TECHNICAL SECTOR Ir (lll) luminescent complexes of the present invention have potential application in very diverse fields. In the pharmacological sector, for the development of new drugs effective in the chemotherapeutic treatment of some types of cancer with intrinsic resistance or acquired to the available treatments. In biotechnology, in the design of new luminescent bio-probes for the visualization of organelles and cellular processes by confocal fluorescence microscopy. In analytical chemistry, to obtain new sensors useful in the selective detection of certain analytes of interest by luminescent procedures. In the electronic industry, for the development of electroluminescent devices of OLED and LEC type useful in the manufacture of flat screens or lamps and other lighting elements. In the energy sector, for the development of efficient photocatalysts in the generation of hydrogen, as an energy vector from water and also in the manufacture of more efficient photovoltaic cells.
BACKGROUND OF THE INVENTION Ir (HI) triskelate complexes, both biscyclomethalated and triscyclomethalated, have luminescent properties that make them promising components in optoelectronic systems. Particularly important are the properties of monocathionic Ir (lll) compounds with orthometalated ligands (Ch. D. Sunesh, G. Mathai, Y. Choe. "Constructive effects of Long Alkyl Chains on the Electroluminiscent Properties of Cationic Iridium Complex-Based Light-Emitting Electrochemical Cellsquot; ACS, Applied Materials & Interfaces 2014, 6,17416-17425).
WO 2006/51810 A1 describes Ir (lll) compounds of the general formula (Ir (NANAN) (CNhl with Iridelated Terpiridine-type (NANAN) ligands and cyanide ligands applied to the manufacture of blue light emitting devices. These compounds are they differ from those described in the present invention in neutral ligands, which are terpyridines instead of arylazoles of the invention, and also in formally anionic ligands that are cyanides instead of phenylpyridinates of the invention.
US 201010108994 A1 describes the preparation of Ir (lII) complexes with orthometalated arylbenzotriazoles of the general formula [lr (Cquot; NhJ, [lr (Cquot; Nh (Oquot; N)) or [lr (CAN), (OAO)] (CAN) = arylbenzolrizolalo, (OAO) = ~ -dicelonalo, (Oquot; N) = hydroxyphenylbenzoazole) for use in the preparation of OLEO devices,
5 as oxygen sensitive or phosphorescent indicators in bioassays and as catalysts.
US 8,039,123 82 also uses benzotriazoles to build Ir (III) -Cu (l) heterodinuclear molecular systems with good efficiency as emitters
lOin the color red. On the contrary, the complexes of the present invention are mononuclear Ir (II I), the use of which is in no way suggested by the document.
Application WO 20101056066 A1 describes several neutral compounds of Ir (lIl) of
15 general formula [lr (Cquot; NhJ with heteroleptic cyclomethalated ligands, [lr (CAN), (NAN)] (CAN) = arylpyridinate, (NAN) = pyridylimidazolate) and [lr (CAN), (OAO)] ( Cquot; N) = arylpyridinate, (0quot; 0) = B-diketonate), where the emission energy is modulated from blue to red. All the complexes obtained are neutral. The scope of the present invention includes some neutral complexes, but they differ in the type of
20 auxiliary ligands "Oquot; N) = hydroxyphenylazolates) of those described in the publication although the spectrum of light in which they emit is very broad in both cases.
US 2013/0056716 A1 describes bis (cyclomethalated) cationic complexes of Ir (lIl) of the general formula [lr (Cquot; Ch (Nquot; N ')] A, where (Cquot; C) is a cyclomethalated carbine type 25 ligand, ( N ') in a di-imine auxiliary ligand and A is a contraction. These complexes are applied in the elaboration of emitting devices capable of converting electrical energy into light very efficiently, for use in the manufacture of digital screens and lighting panels The presence of cyclomethalated carbine-type ligands (Cquot; C) is the main difference with respect to the present invention, which
30 incorporates cyclomethalated ligands of type (Cquot; N). Auxiliary ligands (Nquot; N ') of the arylazole type also differ from those used in the invention, which exhibit greater variability.
Therefore, the problem that arises in the art is the obtaining of complexes of Ir (lIl) alternative to the existing ones. The solution provided by the present invention is the
inclusion of newauxiliary ligands (Nquot; O) or (Nquot; N ') to obtain complexes of
general formula [lr (C'N), (N'O)) or [Go (C'N), (N'N ')) A.
DESCRIPTION OF THE INVENTION
5 TheinventionThey aresomecomplexesfromGo (!! I)fromformulageneral (Go (Cquot; Nh (Nquot; O))or
[lr (C'N), (N'N ')) A, in that Aisaanion, each (C'N)isacyclometalated ligand
independent and (Nquot; O) or (NAN ') isaarylazole ligand.Thearylazole ligandsThey are
typically neutral in the case of (NAN ') or anionic for (Nquot; O).
I O Inapreferable aspect of the invention said anionisamonoanionic anion. The
structure of the moleculeyou acceptanyanionmonoanionic but theinvention
preferably contemplates halide, hexafluorophosphate (PF6-),tetrafluoroborate(BF4-),
tetraphenylborate (BPh4-) or tosylate (TsOquot;). In another more preferable aspect, said halide
It's chlorine.
fifteen
In a very preferable aspect, the invention is a complex of Ir (lll) of general formula
(Go (Cquot; Nh (Nquot; O)] or [lr (Cquot; N) z (Nquot; N ')] A where A is an anion selected from a halide,
hexafluorophosphus (PF,), telrafluoroboralo(BF¡),tetraphenylborate(BPh¡)ORtosilalo
(TsO-), each (CAN) is a cyclomelated ligand independently selected from
twenty between: lt; ) lt; )
equot;
Hooe
or quot; quot;
ce) lt;)
I 0
H
and (N / ID) or (Nquot; N ') is an arylazole ligand selected from the group consisting of:
5 where Y is OH or NH2, and X is NH, N-Me, S or O;
in which X is NH, N-Me, S or O;
10
in which X is N-H, N-CHquot; N-CH, Ph, O or S;
fifteen where X is N-CH, Ph, O or S;
,Y
being that the ligands (N quot; O) are part of the complex in its deprotonated form.
The deprotonated form of said ligand (NAO) corresponds to the anionic form once the hydrogen has been removed from the hydroxyl group, capable of reacting with Ir (lIl) to form the complex.
All the complexes of the invention have surprising photo-physical properties, such as high Stokes displacements, long life times for excited states, excellent quantum yields and great versatility in the emission wavelength modulation.
Orthometalated ligands (CAN) provide high stability to complexes and durability to devices manufactured from them, also participating as modulators in light emission properties. The ligands (NAO) or (NAN ') characteristic of the invention extend the modulation capacity of the energy emitted by the compound without decaying in the excellent intensity of the phosphorescence and improve the emission times and the efficiency of the absorbed energy.
Regardless of its modulation, the diversity of ligands (NAO) or (NAN ') used allows a family of compounds that emit light from blue to orange, covering much of the visible spectrum. In addition, some ligands (NAO) or (NAN '), and also others (CAN), have acidic NH or OH groups that can be reversibly deprotonated or that can interact with other chemical species via hydrogen bonds. These modifications in the structures or chemical environments of these compounds translate into variations of the corresponding photophysical properties, particularly in the color of the emission and the quantum yield, which opens a wide range of possibilities of technological application allowing to improve the current conversion. photon in LEC devices, the photocatalytic action of the complexes by altering and modulating their electrochemical potentials, the photoluminescent activity in biological application devices (phosphorescent probes in living cells, photodynamic cytotoxicity, marking and signaling of proteins for monitoring, etc.) or analytical (proton and ion or molecule probes).
The modular structure of the compounds of the invention allows the 2 types of ligands (C'N) and (N'O) or (N'N ') to be modified independently. The arylazole (N quot; O) or (Nquot; N ') ligands can be easily functionalized in different positions and using different synthesis strategies, which gives access to a large number of compounds and allows for an on-demand modulation of the properties physicochemical and photophysical.
The synthesis process described in the art for iridium fluorescent compounds of similar structure to the invention comprises two steps that are carried out by conventional reflux reactions at high T and with long reaction times.
The Ir (lIl) compounds of the invention, both cationic, [lr (CI Nh (Nquot; N ')] A, and neutral, [lr (Cquot; Nh (Oquot; N)] (where Cquot; N = cyclomethalated monoanionic ligand of the phenyl-pyridinate type, Nquot; N '= neutral ligand of di-imine type, Nquot; O = monoanionic ligand of the aryl-phenolate type, all bidentate), comprise a great diversity of ligands that are capable of modulating the energy of the luminescence over a wide range, covering much of the visible spectrum.
In particular, the ligands (Nquot; O) bind to the metal center in its monoanionic form azolylphenolate obtained by deprotonation from the corresponding neutral proligands type hydroxyphenylazole. In this case, the resulting complexes are very sensitive to pH and may experience degradation by protonation and subsequent dissociation of the ligand at acidic pH. Cquot; N ligands, on the other hand, bind to the metal center more robustly and do not suffer dissociation at acidic pH. This circumstance should be taken into account in the possible applications of the aforementioned metal derivatives.
Table 1 shows the main photophysical properties of the ligands used and the complexes prepared. These properties have been recorded using the excitation wavelengths indicated in the table for 10-4 M solutions in acetonitrile. The quantum yield of the compounds of the invention is always
~
.- 'quot; ¡[
lt; quot; gt;
or
or
'quot;
quot;
and
quot;
quot;
quot;
quot; O
quot;
iD
~.
quot; ~
~
¡;;
OR;
Cgt;
¡;;
Ligand (CAN) <; Ogt; - <; C: P --- <; Ogt; - CJgt; , - d-o cPbgt; 0-8ppy Ipy dlppy bq piq
Dimer of Partid to [lrCI (CAN) 2J, A.quot; (nm) = 375 385 397 A.m (nm) = 509 476 546 $ (%) = 1.55 1.69 1.22
Auxiliary Ligand (N AO), or (NA N) ' [lr (ppy), (N AN)] CI [lr (lpy), (N AN)] CI [Go (dlppy), (NA N)] CI [lr (bq), (N AN)] CI [lr (piq), (N AN)] CI
Q -lt;, ::: r: :) '-' (nm) 'quot; 329, A.m (nm) = 359 (UV), 41 (%) = 129.82 "; 376 381 381 378 469 563 (yellow-green) 570 (yellow) 504 (green) 558 (green) 594 (orange) 14.78 11.59 31.45 12.10 37.98
O-lt; :: sJ '-' (nm) 'quot; 329 A.m (nm) = 361 (UV), 41 (%) = 132.45- 382 382 576 (yellow) 587 (yellow-orange) 17.12 12.75
cgt; - lt; .Nquot; JN, quot; 398 511 (green) 89.03
o-lt; :: C:;: gt; '-' (nm) 'quot; 320, '(nm) = 351 (UV) 4gt; (%) = 62.87 397 628 (orange) 0.613
'quot; e quot; o quot; 6 '~ quot;
~ or F quot; ~
quot; quot; ' e ~ g
lt; quot; gt; quot; 'quot; or 'quot; 'quot; e quot; O
~ o '~
~
w o quot; quot; o o 5 '<gt; E 'quot; Or 3 ";" quot; quot; '
iquot; quot; or quot; 6 '~
~
Ogt; or quot; quot; or ~ quot; ~~ 6``1 'f'm
~ w
~ m m ~
or ólt;: -: ú quot; , quot; b
S ~ N '~
quot;
'quot; lt; = gt; -lt; quot; -lt; quot; ~,
- (
quot;
6lt; .-, '~
, ~
,
A ..,. Or (nm) 'quot; 369 I
A.m (nm) 'quot; 400 (viol.) «Quot; lo) = 10.19
A.:c (nm) = 317 I quot ;-( nm) = 352 (UV) $ (%) 'quot; 8.60
! .. <lom). 286 I
), ...., (nm) = 311 (UV) ojI (%) = O, 10
A.:c (nm) = 338 I
A.m (nm) = 457 (blue) 41 (%) quot; ' 63 DO NOT SOLUBLE
482 (blue) 25.39
378591 (orange)0.33
533 (green)
95 359
402,531 4.99
398481 (eano)26.88
400533 (green)0.71
527 (green)
404 (violet) 6.47
340483 (eano)14.79
533 (green)
9.68
512 (green)
85 372
537 (green)
5.97
532 (green)
52.95
577 (yellow)
0.51
469593 (orange)37.32
440590 (orange)12.22
,}) H A ..,. C (nm) = 311 I 469 469 451 lt; =: gt; -lt; N ~), ...., (nm) = 363 (UV)
605 (orange) 607 (orange) 580 (orange) -s «%) = 0.2
11 9 30
The process for obtaining the cationic complexes of Ir (lIl) of the invention
5 It comprises two stages: a) First stage of the synthesis. Obtaining the dimeric starting products of the general formula [(Cquot; Nhlr (u-Cnh.
1 o The process of the art for preparing this type of products involves the use of reflux in a mixture of 2-ethoxyethanol and water as solvents with high reaction temperatures and with reaction times greater than 24 hours.
fifteen In the present application an alternative synthesis process is described for some of these products with microwave radiation as an energy source, which constitutes a further aspect of the invention. The reaction is carried out by reaction between IrCb · 3H2ü and the precursor of the cyclomelated ligand HCquot; N (See structures H1 to HLg in Table 1) using an approximate 1: 2 molar ratio.
twenty The new procedure has been used for example (where CAN = L ', L4 and L' (Table 1, scheme 1 (a ».inthe products [lr2CI2 (Cquot; N) 4]
The solvents are 2-ethoxyethanol l water in a 3: 1 ratio.
Dissolvcntcs
J
6. Microwave &) -F- {S (J; () (NJ
dfppyH
This procedure allows reaction times of less than 1 hour. In addition, it improves the yields and purity of the products since no products are formed
minor or minor isomers, but the essentially pure desired product is obtained. It thus presents the technological advantages of avoiding purification processes and reducing energy consumption and the use of organic solvents.
5 The following precursors were thus synthesized as cyclomethalated ligands (CflN)
(THE):
HL 'H HL' H
Hoce
H H
HL 'HL' HHL '
H, N
r ~~ eX) ~)
rN
- H, N H H ~ H
HL 'HL' HL '
That after deprotonation resulted in the corresponding active ligands to be bound to Ir (III), as follows:
•
F CH, () <; )
G G
L 'L' L '
HOOC
j
LL 'O O
G
L '
H, N ~) ~) ex) lt ;.)
O o
I G
G
H2N L7 H
L 'L'
b) Second stage of the synthesis. Obtaining the cyclometalated complexes5 mononuclear of the invention.
The final Ir (llI) cyclomelated products are obtained from the dinuclear starting products of the general formula [(Cquot; Nhlr (). L-CI ») z by direct reaction with the auxiliary ligands of type (Oquot; N) or (NAN '), using conventional procedures
10 consisting of heating the reagents in 2-ethoxyethanol! water (1: 1) at temperatures in the range between 110-140 oC and in the presence of sodium carbonate (NazCOJ) as a base for type ligands (OAN), or in a mixture of methanol dichloromethane (5: 4) at 65 oC, for type ligands (NI N ').
According to the preferable aspect, the chloride ion is represented in the following scheme, although the procedure is valid with any other anion and more preferably those specified in the present invention.
Dissolve
•
The structure of the di-imine, amino-imine (NAN ') or hydroxyimine (Oquot; N) auxiliary ligands used in the synthesis of Ir (lIl) complexes is as follows:
X: NH, N-Me, S, O
Y: NH2, OH¡; -N N ~ 'V-<; x.J.J
X: NH, N-Me, 5 ° N N ------ (NH,
v quot; ':: {/ N C) --- lt;
- N (
NH,
EXAMPLES lt; ) <N ~
X
X: N-CH2Ph, 0, S
10 With the intention of showing the present invention in an illustrative way but in no way limiting, the following examples are provided_
Commercial suppliers of iridium salt (IrCh-3H20), and auxiliary ligands and cyclometalating pro-ligands used in the present invention are the following:
Iridium (llI) Chloride, IrCI, '3H, O (Johson Matthey).2-phenylpyridine (Aldrich).2- (p-Tolyl) pyridine (Aldrich).
20 2- (2,4-Difluorophenyl) pyridine (Aldrich) 2-Phenylquinoline (Aldrich) Benzo [h] quinoline (Aldrich) 2-phenylbenzimidazole (Aldrich) 2,4-diamino-6- (phenyl) -1, 3, 5-triazine (Aldrich).
2- (4-thiazolyl) benzimidazole (Aldrich). 2- (2-aminophenyl) -1 H-benzimidazole (Aldrich)
2- (2-aminophenyl) -1 H-benzothiazole (Aldrich) 2- (2-hydroxyphenyl) -1 H-benzimidazole (Aldrich)
5 2- (2-hydroxyphenyl) -1 H-benzothiazole (Aldrich)
8-aminoquinoline (Aldrich).
2,4-diamino-6- (2-pyridyl) -1, 3,5-triazine (Aldrich).2-Phenyl-4-quinolinecarboxylic acid (Aldrich).
The auxiliary ligands prepared according to the procedures described in the corresponding literature are referenced below:
2- (pyridyl) imidazole (Peng, X .; Deng, J.-G .; Xu, H.-B. RSC Adv. 2013, 3, 24146). 2- (2-Pyridyl) benzoxazole (Chen, F .; Shen, C .; Yang, D. Te / rahedron Le //. 2011,
15 52, 2128-2131). 2- (4-lhiazolyl) -N-melhylbenzimidazole (Rel: Zeng, F. L .; Yu, Z. K. Organome / allics 2008, 27, 2898-2901). 2- (2-aminophenyl) -N-melhyl-benzimidazole (Rel: Zeng, F. L .; Yu, Z. K. Organome / allics 2008, 27, 2898-2901).
20 2- (2-hydroxyphenyl) -N-melhyl-benzimidazole (Rel: Zeng, F. L .; Yu, Z. K. Organome / allics 2008, 27, 2898-2901).
2-Phenylisoquinoline (Ref: Liu, C .; Ni, Q .; Hu, P .; Qiu, J. Org. Biomal. Chem.
2011, 9, 1054-1060).1- (pyridin-2-yl) -N- (quinolin-3-yl) melhanimine (Rel: Bahner, Carl Tabb;
25 Brotherton, David: Brotherton, Mary Karasek, Journal of Medicinal Chemistry (1968),
11 (2), 405-6).2- (pyridyl) -N-phenylbenzimidazole (Rel: Cao, Q .; Bailie, D. S .; Fu, R.; Muldoon,
M. J. Green Chem. 2015, 17, 275 () - 2757).
30 Example 1: Synthesis of precursors
The products have been synthesized (Ir, CI, (CAN), l (where (CAN) = L ', L' Y L '(Table 1, andscheme 1 (a ».Synthesis of the precursor [lr (L 2h (~ -CI)],
A suspension of IrCl3.3H20 (352 mg, 1.0 mmol) in 16 mL of a previously deoxygenated mixture of 5 2-ethoxyethanol / water (3: 1, v / v) is prepared in a 100 mL Schlenk flask under an inert atmosphere. The pro-ligand 2- (2,4-difluorophenyl) pyridine, HL2, (378 ~ L, 2.5 mmol) is then added, while stirring the mixture for 5 minutes to homogenize. It is transferred to a 20 mL microwave vial (in an inert atmosphere, using a sample) using a pipette. If the transfer is not complete, 1-2 mL of solvent mixture is used to rinse the 10 Schlenk. A stirring magnet is added, the vial is sealed and taken to the microwave. The reaction is carried out under the following conditions (Equipment
Biotage Start):
Temperature: 200 oC (15 bar).Time: 60 minutes
15 Vial: 10-20 mL. Pre-agitation: 1 minute. MW absorption: high.
The mixture obtained is then allowed to cool to room temperature and is
20 Transfers into a Schlenk flask under nitrogen atmosphere (sample preparation). The mixture is concentrated in vacuo to a quarter of its volume; 20 mL of deaerated water are added and filtered by washing the yellow solid with two 8 mL portions of hexane. The product is dried under vacuum for 4 hours at 65 oC. 85% yield.
25 Synthesis of the precursor [lr (L8), (~ -CI)],
A suspension of IrCI3.3H20 (352 mg, 1.0 mmol) in 16 mL of a previously deoxygenated mixture of 5 2-ethoxyethanol / water (3: 1, v / v) is prepared in a 100 mL Schlenk flask under an inert atmosphere. Then the pro-ligand benzo [h] quinoline, HL8, (448 mg, 2.5 mmol) is added, while stirring the mixture for 5 minutes to homogenize. It is transferred to a 20 mL microwave vial (in an inert atmosphere, using a sample) using a pipette. If the transfer is not complete, 1-2 mL of solvent mixture is used to rinse the 10 Schlenk. A stirring magnet is added, the vial is sealed and taken to the microwave. The reaction is carried out under the following conditions (Equipment
Biotage fniciator):
Temperature: 200 oC (15 bar).Time: 60 + 30 minutes.
15 Vial: 10-20 mL. Pre-agitation: 1 minute. MW absorption: high.
The mixture obtained is then allowed to cool to room temperature and is
20 Transfers into a Schlenk flask under nitrogen atmosphere (sample preparation). The mixture is concentrated in vacuo to a quarter of its volume; 20 mL of deaerated water are added and filtered by washing the yellow solid with two 8 mL portions of hexane. The product is dried under vacuum for 4 hours at 65 oC. 80% yield.
25 Example 2: Synthesis and characterization of the complex [lr (L 1h (pyim)] CI In a 100 mL Schlenk flask, on a solution of the dimeric product
5 [lr (ppy), CI], (0.1002 g, 0.093 mmol) in 7.5 mL of dry and distilled methanol, ligand 2- (2'-pyridylimidazole) (0.0312 g, 0.193 mmol, 90% purity) was added together with 6 mL of
dichloromethane The mixture was left under stirring for 24 hours at 60 ° C. The solution was filtered to discard solid impurities, and the desired product was precipitated by adding diethyl ether. It was collected by filtration, washed with ether and dried under vacuum. It was obtained
10 a yellow solid. Yield: 80%. The spectroscopic and characterization data of the complex obtained were the following:
M, (C30Hquot; N, Cllr) = 681.2179 g / mol.
Elemental analysis (%) calculated for C30Hz3N5Cllr · (CH30H) 1.2 (CHzClz) o.z: C 51 .20;
15 H 3.86; N 9.51; Found: C 51 .13; H 3.79; N 9.05.
'H NMR (400 MHz, CDCIquot; 25' C) and 15.88 (s, 1H, HN-quot;), 9.38 (dd, J = 8.1, 0.8 Hz, 1H,H '), 7.95 (t, J = 7.8 Hz, 1H, Hquot;), 7.87 (dd, J = 8.1, 1.3 Hz, 2H, H', H '), 7.79-7.69 (m,3H, Hquot; , H ', H'), 7.66 (d, J = 7.1 Hz, 2H, H ', H'), 7.63 (d, J = 7.7 Hz, 1 H, H '), 7.50 (dd, J20 = 5.8, 0.7 Hz, 1H, H '), 7.33 (s, 1H, Hquot;), 7.21 -7_16 (m, 1H, H'), 7.03 -6.92 (m, 4H,H ', H', H ', H'), 6.89 (1, J = 7.4 Hz, 1H, H '), 6.84 (t, J = 7.4 Hz, 1H, H'), 6.51 (s, 1H, H '), 6.40 (d, J = 7.6 Hz, 1H, H '), 6.31 (d, J = 7.6 Hz, 1 H, H') ppm.
quot; C {'H) NMR (101 MHz, COCIquot; 25' C) O 168.31 (s, 1C, C '), 168.28 (s, 1C, C'), 152.2
25 (s, 1C, C '), 149.9 (s, 1C, c'), 149.1 (s, 1C, c '), 148.8 (s, 2C, c', C '), 148.6 (s, 1C, c '' j, 148.4 (s, 1C, c '' j, 147.6 (s, 1C, C '), 144.2 (s, 1C, C'), 143.8 (s, 1C, C '), 139.5 (s, lC , c '), 137.7 (s, lC, CS), 137_6 (s, lC, c'J, 132.2 (s, l C, C'), 132.0 (s, l C, C '), 130.7 (s, 1C, C '), 130.2 (s, 1C, C'), 127.2 (s, 1C, C '' j, 125.8 (s, 1C, CS), 124.8 (s, 1C, C '), 124.40 (s, 1 C, C '), 124.36 (s, 1C, c'), 123.0 (s, 1 C, C4), 122.8 (s, 1 C, C4), 122.3 (s, 1C, C '), 122 .1 (s, 1C, C '), 11 9.3 (s, 2C, c', C ') ppm.
Example 3: Synthesis and characterization of the complex [lr (L1h (pybox)] CI
On a solution of [lr (ppy), CI], (0.0785 g, 0.073 mmol) in 7.5 mL of dry and distilled methanol in a Schlenk flask, ligand 2- (2'-pyridylbenzoxazole) 10 (0.0303 g, 0.154 mmol), together with 6 mL of dichloromethane. Everything is left under agitation
for 24 hours at 60 ° C. The solid is precipitated by adding diethyl ether and allowed to stir. Filter and wash with ether. It dries under vacuum. An orange solid is obtained. Yield: 69%.
M, (C34H, .N40Cllr) = 732.2625 g / mol.
15 Elemental analysis (%) calculated for C34H24N40Cllrquot; (CH30Hks (CH2CI2} o.s: C 52.16: H 3.78: N 6.74: Found: C 52.26: H 3.71: N 5.88.
'H NMR (400 MHz, COCI, 25' C) OR 8.90 (d, J = 7.8 Hz, 1H, H '), 8.69 (t, J = 7.7 Hz, 1H, H4), 7.94 (d, J = 6.7 Hz, 2H, H ', H' '), 7.87 (d, J = 8.4 Hz, 1H, H'), 7.79 (m, 5H, Hquot ;, H4 H4
20,, Hquot ;, H '), 7.70 (t, J = 7.2 Hz, 2H, H', H '), 7.62 (d, J = 5.6 Hz, 1H, H'), 7.53 (t, J =
8.0 Hz, 1H, H '), 7.21 (t, J = 7.8 Hz, 1H, H'), 7.17-7.08 (m, 2H, H ', H'), 7.08 -7.03 (m, 2H, H ', H '), 6.99 -6.91 (m, 2H, H', H '), 6.44 (d, J = 7.7 Hz, 1H, HI), 6.33 (d, J = 7.6 Hz, 1 H, H '), 6.30 (d, J = 8.2 Hz, 1H, H') ppm.
25 quot; C {IH} NMR (101 MHz, COCI, 25 'C) OR 167.9 (s, 1C, C'), 167.8 (s, 1C, C '), 166.8 (s, a · b · s · S s
1C, C), 151.6 (s, 1C, C), 151.4 (s, 1C, C), 149.6 (s, 1C, C), 149.4 (s, 1C, C), 148.2 (s, 1C , C '), 144.46 (s, 1C, C'), 144.43 (s, 1C, Cb), 143.7 (s, 1C, Cb), 143.1 (s, 1C, c '),
4 · 4 4 g.
142.0 (s, 1C, C), 138.53 (s, 1C, C), 138.48 (s, 1C, C), 137.4 (s, 1C, C), 132.6 (s, 1C, CI), 131.7 (s, 1C , C '), 131.2 (s, 1C, c'), 131.1 (s, 1C, C '), 130.3 (s, 1C, C'), 128.9
(s, 1e, e d), 127.8 (s, 1e, equot;), 127.6 (s, 1e, e '), 125.1 (s, 1e, e'), 124.6 (s, 1e, e '),
124.0 (s, 1 e, eS), 123.8 (s, 1 e, eS), 123.2 (s, 1 e, ed), 123.1 (s, 1 e, ed), 119.6 (s, 1 e, e ') , 119.5 (s, 1 e, e '), 118.7 (s, 1e, e'), 113.1 (s, 1e, equot;) ppm.
5 FT-IR (KBr, cmquot;): 3284 (w), 3041 (w, Ve.eH), 1604-1583 (m, see eg eN), 1479 (s), 14381420 (m), 1389 ( s), 1269 (m), 1166 (m, ve.e), 1092-1065-1032-1017 (m, Óe.Hi), 813800 (w), 759-740 (vs, Óe.Hoo,), 630 (m). MS (FAB +): miz ('lo) = 698 (100) ([M-el + Hn, 501 (40) ([M-el-pybzOxf). Molar conductivity (CH 3CN): 112 S · cm2 · mor1.
10 Solubility: soluble in methanol dichloromethane, chloroform and acetone.
Example 4: Synthesis and characterization of the complex [lr (L 1h (tbz}] CI)
On a solution of [lr (ppy), CI], (0.1001 g, 0.093 mmol) in 7.5 mL of dry and distilled methanol in a Sehlenk flask, the thiabendazole ligand (0.0375 g, 0.186 mmol), together with 6 mL of dichloromethane. Everything is left under agitation during
20 20h at 60 ° C. The solid is precipitated by adding diethyl ether. Filter, wash with ether and dry in vacuo. A yellow solid is obtained. Yield: 82%.
Spectroscopic and characterization data
M, (Cquot; Hquot; NsSCllr) = 737.3069 glmol.
Elemental analysis (%) calculated for C32H23N4SCllrquot; (CH2CI2) o.r (H20) o.8: e 49.27; H
25 3.29; N 7.03; S 4.02; Found: e 49.32; H 3.33; N 9.11; S 4.19.
Elemental analysis (%) calculated for C32H23N4SCllr- (CH30H} o.7 (CH2Cb) I) .8: e 49.45; H 3.39; N 6.89; S 3.94; Found: e 49.32; H 3.33; N 9.11; S 4.19.
'H NMR (400 MHz, CDCIquot; 25' C) ~ 15.73 (s, 1 H, HN.H), 10.09 (d, J = 1.3 Hz, lH, H ''), 8.13 (d, J = 2.1 Hz , 1 H, H5 '), 7.89 (d, J = 8.7 Hz, 1 H, H'), 7.85 (d, J = 7.8 Hz, lH, H '), 7.78 (d, J = 8.2 Hz, lH, Hquot;), 7.76 -7.70 (m, 2H, H ', H'), 7.70 -7.62 (m, 3H, H ', H', H '), 7.52 (d, J = 5.8 Hz, lH, H' ), 7.25 (1, J = 8.2 Hz, lH, Hd '), 7.07 (1, J = 7.5 Hz, lH,
5 Hd), 7.00 (1, J = 7.5 Hz, 1 H, Hd), 6.98 -6.85 (m, 5H, Hquot ;, H5, H5, H ', H'), 6.45 (d, J = 7.9Hz, 1 H, H '), 6.40 (d, J = 7.3 Hz, 1 H, H'), 6.16 (d, J = 8.3 Hz, 1 H, H ') ppm.
quot; C {'H} NMR (101 MHz, COC! Quot; 25' C) ~ 168.4 (s, 1 C, C2), 168.1 (s, 1 C, C2), 155. 1 (s, lC, C5 ') , 149.8 (s, lC, C '), 148.6 (s, lC, C'), 148.29 (s, lC, C '), 148.25 (s, lC, c2'), 10 146.73 (s, l C, C '), 146.65 (s, l C, C' '), 144.5 (s, lC, Cb), 144.3 (s, lC, Cb), 139.8 (s,
g '4 4 ti' f
le, C), 137.9 (s, l C, C), 137.7 (s, l C, C), 134.9 (s, l C, C), 132.5 (s, l C, C), 132.3 (s, lC , C '), 130.5 (s, l C, C'), 130.1 (s, l C, C '), 125.6 (s, l C, Cquot;), 125. 1 (s, l C, Cd') , 124.59 (s, l C, C '), 124.56 (s, l C, C'), 124.2 (s, l C, Cquot;), 123.2 (s, lC, C5), 122.9 (s,
lC, C5), 122.5 (s, 1 C, Cd), 122.4 (s, 1 C, Cd), 119.3 (s, 2C, C ', C'), 117.1 (s, 1 C, C '), 15 11 4.4 (s, l C, C '') ppm.
FT-IR (KBr, cm- '): 3372 (w, VN.Hquot; OOquot ;,'), 3034 (w, Ve ~ eH), 2618 (w, V.eH), 1606-1 579 (m,
ve ~ e.e.,.), 1476 (s), 1455 (w, Ve ~ N), 1416 (s), 1267 (m), 1227 (m) 11 61 (m, ve.e), 1060
1030-1011-994 (m, ~ e · H'p), 830 (m), 795 (w, ~ ed, 751 (vs, ~ e · Hoop), 630 (m), 560 (m),
20 436-421 (m). MS (FAB +): miz (%) = 1404 (3) ([2M-2CI] '), 703 (100) ([M-CI + H]'), 501 (58) ([M-Cll hbzolJ ') . Molar conductivity (CH, CN): 21 5 · cm2 · mol '.
Solubility: soluble in methanol dichloromethane, chloroform and acetone, partially soluble in methanol and insoluble in water,
Example 5: Synthesis and characterization of the complex [lr (L 'j, (pydaT)] CI
On a solution of [lr (ppy), CI], (0.1001 g, 0.093 mmol) in 10 mL of methanol
Distilled and dried in a Schlenk flask, the 2-pyridyldiamiotriazine ligand (0.0360 g, 0.191 mmol) is added, together with 8 mL of dichloromethane. Everything is left under stirring for 24 hours at 60 ° C. The solvent is evaporated to dryness and the residue is washed with
5 hexane Filter and dry in vacuo. An orange solid is obtained. Performance:94%
Spectroscopic and characterization data
M, (C30Hquot; N, Cllr) = 724.2459 glmol.
Elemental analysis (%) calculated for CloH24NsCllr (H20h: C 46.30; H 3.89; N
10 14.40; Found: C 46.26; H 3.86; N 14.61.
'H NMR (400 MHz, DMSO-dquot; 25' C) or 8.57 (d, J = 7.8 Hz, lH, Hquot;), 8.38 -8.31 (m, 2H, H ', H'), 8.31 -8.23 ( m, 2H, H ', H'), 8.07 -7.92 (m, 3H, H ', H', H '), 7.89 (d, J =
7.5 Hz, 2H, H ', HNH2 (quot;'), 7.81 (s, lH, HNH2 (quot; '), 7.79-7.73 (m, 2H, Hquot ;, HNH2 (o'), 7.70 (d, J 15 = 4.8 Hz, 1 H, H '), 7.54 (d, J = 5.3 Hz, 1 H, H'), 7.31 (t, J = 6.5 Hz, 1 H, H '), 7.25 (t, J =
6.6 Hz, lH, H '), 7.00 (t, J = 7.5 Hz, 2H, H', H '), 6.87 (q, J = 6.6 Hz, 2H, H', H '), 6.18 (d, J = 7.3 Hz, lH, H '), 6.00 (d, J = 7.4 Hz, 1 H, H'), 5.30 (s, 1 H, HNH '(, ·,) ppm.
quot; C {'H} NMR (101 MHz, DMSO-dquot; 25' C) or 170.5 (5), 166.6 (s, l C, C '), 166.4 (s, lC,
20 C '), 165.2 (s), 164.9 (s), 154.0 (s, lC, c'), 150.4 (s, lC, C '), 149.3 (s, lC, C'), 148.8 (s, lC , C '), 148.4 (s, lC, C'), 147.2 (s, lC, C '), 144.7 (s, l C, C'), 143.7 (s, lC, C '),
139.6 (s, 1 C, C '), 138.8 (s, l C, C'), 131.5 (s, 1 C, C '), 130.6 (s, 1 C, C'), 130.5 (s, 1 C , c '), 130.4 (s, lC, C'), 130.2 (s, lC, C '), 127.2 (s, lC, c'), 125.6 (s, lC, C '), 125.1 (s, lC , C '), 124.2 (s, 2C, c', C '), 122.7 (s, lC, C'), 122.6 (s, lC, C '), 120.14 (s, lC, C'),
25 120.05 (s, lC, C ') ppm.
FT-IR (KBr, cmquot;): 3377-3323 (w, VN.H '= iquot;'), 3038 (w, Ve.eH), 1605-1577-1558 (m, Ve.e
• e.N), 1505 (s), 1475 (s), 1437-1417-1391 (m), 1265 (m), 1160 (m, vc-e), 1059-1029
995 (m, Óe.Hip), 789 (m, óe.c), 757-731 (vs, Óe.Hoop), 628 (m), 433-403 (m). 30 MS (FAB +): miz (%) = 689 (83) ([M · Cln 501 (25) ([M-CI-pydaTn
twenty-one
Molar conductivity (CH 3CN): 107 S · cm · mor.
Solubility: soluble in water, methanol, dichloromethane, chloroform and acetone.
Example 6: Synthesis and characterization of the complex [lr (L 2h (aPhbzim)] CI
F
On a suspension of [l r (dfppy), (~ -CI) h (100 mg, 0.083 mmol) in 8 mL of methanol
ligand 2- (2-aminophenyl) -1 H-benzimidazole (36 mg, 0.172 mmol) and 6.4 mL is added
5 dichloromethane. The mixture is brought to 60 oC for 24 hours under constant stirring in a nitrogen atmosphere. The mixture is brought to almost dryness in vacuo and the precipitate formed is filtered by washing it with two 8 mL portions of hexane. The product is dried under vacuum for 4 hours at 65 oC. Yield 79%
10 Molecular weight: 817.26 glmol Elemental analysis (%) calculated for C3sH23CIF4IrNs · 1.25H20: C, 50.06; H, 3.06; N, 8.34. Found: C, 50.17: H, 3.12: N, 8.23.
'H NMR (400 MHz, CDCI3 • 25 oC): OR 13.78 (s, 1H), 9.50 (s, 1H), 8.37 (d, J = 8.7 Hz, 15 1H), 8.11 (d, J = 8.8 Hz, 1H), 8.04 (d, J = 7.8 Hz, 1H), 7.91 -7.79 (m, 2H), 7.60 (1, J = 7.9 Hz, 1H), 7.17 (1, J = 6.4 Hz, 1H), 6.89 (t, J = 7.6 Hz, 1H), 6.78 (t, J = 7.3 Hz, 3H),
6.69 (1, J = 6.7 Hz, 1H), 6.61 (t, J = 7.8 Hz, 1H), 6.57 -6.40 (m, 4H), 6.35 (d, J = 8.3 Hz, 1H), 5.68 (d, J = 8.5 Hz, 1H), 5.68 (s, J = 8.4, 1H), 5.56 (d, J = 8.4, 1H), 5.17 (s, 1H).
20 quot; F NMR (376 MHz, CDCI3, 25 oC): OR -107.00 (q, J = 7.63 Hz), -108.03 (q, J = 9.8 Hz),
109.85 (t, J = 10.69), -109.96 (t, J = 10.68 Hz).MS (FAB '): miz (' lo) = 782 (10) [M-CI] ', 573 (10) [M-CI- (apbzim)]'.
Solubility: poorly soluble in chloroform, dimethylsulfoxide, acetone, acetonitrile and
methanol, and insoluble in water.
25 Example 7: Synthesis and characterization of the complex [lr (L ') ¡(tbzH)) CI
"
On a suspension of [Ir (dfppy), (~ -CI)], (100 mg, 0.083 mmol) in 8 mL of methanol, the thiabendazole ligand (35 mg, 0.174 mmol) and 6.4 mL of dichloromethane are added. The
5 mixture is carried at 60 oC for 24 hours under constant stirring in a nitrogen atmosphere. The mixture is brought to almost dryness in vacuo and the precipitate formed is filtered by washing it with two 8 mL portions of hexane. The product is dried under vacuum for 4 hours at 65 oC. Yield 64%.
10 Molecular weight: 809.26 g / mol Elemental analysis (%) calculated for e) 2H1geIF4IrNsS · 2.5H20: e, 45.23; H, 2.79; N, 8.24; S, 3.77. Found: C, 45.53; H, 2.64; N, 8.10; S, 3.94.
'H NMR (400 MHz, CDCIquot; 25 oC): OR 10.15 (s, 1H, H'), 8.32 -8.23 (m, 3H, H ', Hquot ;, Hb),
15 7.84 -7.72 (m, 3H, H ', Hquot ;, Hi), 7.71 (d, J = 5.6 Hz, 1H, H'), 7.48 (d, J = 5.8 Hz, 1H,
6 '' 5 S 'k
H), 7.30 (t, J = 7.8 Hz, 1H, HI), 7.08 -6.97 (m, 3H, H, H, H), 6.62 (t, J = 10.6 Hz,1H, Hquot; '), 6.54 (1, J = 10.7 Hz, 1H, Hquot;), 6.29 (d, J = 8.3 Hz, 1H, H'), 5.84 (d, J = 8.5 Hz,1H, Hquot; '), 5.78 (d, J = 8.3 HZ, 1H, Hquot;).19F NMR (376 MHz, CDCIquot; 25 oC): Ó -106.32 (q, J = 9. 1 Hz, 1F), -106.74 (q, J = 9.1
20 Hz, 1 F), -109.22 (1, J = 11.5 Hz, 1 F), -109.52 (t, J = 11 .5 Hz, 1 F). MS (FAB '): miz (%) = 774 (100) [M-Cr, 573 (95) [M-CI-IbzHf, 494 [M-CI-IbzH-pyf, 383 [Go (dfppy) f, 202 [lbzH, f Solubility: soluble in chloroform, dimethylsulfoxide, acetone, acetonitrile, poorly soluble in methanol and ethanol, and insoluble in water.
25 Example 8: Synthesis and characterization of the complex [lr (L ') ¡(hPhbzim)]
"
On a suspension of [lr (dfppyM¡J-CI)], (100 mg, 0.083 mmol) in a previously deoxygenated mixture of ethoxyethanol / water (1: 1, v / v) ligand 2- (25 hydroxyphenyl) is added benzoliazol (38.5 mg, 0.170 mmol) and Na, CO, (30 mg, 0.283 mmol). The
mixture is brought to 120 oC for 24 hours under constant stirring in a nitrogen atmosphere. The solution is brought to almost dryness in vacuo and the precipitate formed is filtered by washing with water (10 mL), acetone (2 mL) and ethyl ether (2 mL). The product is dried under vacuum for 4 hours at 80 oC.
Molecular Weight: 798.84 g / molElemental analysis (%) calculated for C3sH2oF4IrN30S · 0.5H20: C, 52.04; H, 2.62; N, 5.20; S, 3.97. Found: C, 52.26; H, 2.51; N, 5.10; S, 3.94.
15 'H NMR (400 MHz, DMSO-dquot; 25 oC): O 8.91 (d, J = 4.9 Hz, 1H), 8.31 (d, J = 5.8 Hz, 1H), 8.28 (d, J = 8.6 Hz, 1H), 8.15 (d, J = 8.6 Hz, 1H), 8.04 -7.95 (m, 2H), 7.91 (1, J = 7.8 Hz, 1 H), 7.53 (d, J = 8.0 Hz, 1 H), 7.36 (1, J = 6.7 Hz, 1H), 7.23 (1, J = 7.6 Hz, 1 H),
7. 16 (1, J = 6.8 Hz, 1H), 7.05 (1, J = 8.7 Hz, 1H), 6.99 (1, J = 8.5 Hz, 1 H), 6.89 (d, J = 8.6 Hz, 1 H ), 6.80 -6.70 (m, 2H), 6.42 (1, J = 7.5 Hz, 1 H), 6.35 (d, J = 8.5 Hz, 1H), 5.77 (dd,
20 J = 8.9, 2.5 Hz, 1 H), 5.27 (dd, J = 8.8, 2.4 Hz, 1H). quot; F NMR (376 MHz, DMSO-dquot; 25 oC): O -108.69 (q, J = 9.7 Hz, 1F), -108.96 (q, J = 9.3 Hz, 1F), -109.82 (I, J = 11.7Hz, 1F), - 11 1.16 (t, J = 11.3 Hz, 1F). MS (FAB '): miz (%) = 799 (91) [M]', 573 (100) [M- (opbzti ») '.
Solubility: soluble in chloroform, poorly soluble in dimethylsulfoxide, acetone, acetonitrile and methanol, and insoluble in water.
Example 9: Synthesis and characterization of the complex [lr (L2h (hPhbztz)]
On a suspension of [lr (dfppyM¡J-CI)], (100 mg, 0.083 mmol) in a mixture
previously deoxygenated ethoxyethanol / water (1: 1, v / v) ligand 2- (2
5-hydroxyphenyl) -1 H-benzimidazole (37 mg, 0.176 mmol) and Na, CO, (30 mg, 0.283 mmol). The
mixture is brought to 120 oC for 24 hours under constant stirring in a nitrogen atmosphere. The solution is brought to almost dryness in vacuo and the precipitate formed is filtered by washing with water (10 mL), acetone (2 mL) and ethyl ether (2 mL). The product is dried under vacuum for 4 hours at 80 oC. Yield 73%.
Molecular Weight: 781.79 g / molElemental analysis (%) calculated for e 3sH21eIF4IrN40 · 1.25H20: e, 52.27; H, 2.94;
N, 6.97. Found: C, 52.50; H, 2.70; N, 6.88.
15 'H NMR (400 MHz, DMSO-dquot; 25 oC): O 13.09 (s, 1 H), 8.85 (d, J = 6.1 Hz, 1 H), 8.21 (d, J = 8.4 Hz, 1H), 8.17 (d, J = 8.5 Hz, 1H), 8.1 1 (d, J = 5.9 Hz, 1H), 7.96-7.82 (m, 2H), 7.71 (d, J = 8.4 Hz, 1H), 7.43 (d, J = 8.0 Hz, 1H), 7.32 (1. J = 6.7 Hz, 1H), 7.11 (1, J =
6.6 Hz, 1H), 7.05 (t, J = 7.5 Hz, 1H), 6.99 (1, J = 6.8 Hz, 1H), 6.81 -6.63 (m, 3H), 6.47 -6.35 (m, 2H), 6.19 ( d, J = 8.4 Hz, 1H), 5.77 (d, J = 8.9 Hz, 1H), 5.39 (d, J = 8.6 Hz,
20 1H). quot; F NMR (376 MHz, DMSO-dquot; 25 oC): O -109.18 (q, J = 9.2 Hz, 1F), -109.47 (q, J = 9.2 Hz, 1F), -11 0.46 (1, J = 11 .1 Hz, 1F), -11 1.39 (1, J = 11.2 Hz, 1F). MS (FAB '): miz (%) = 782 (8) [Mf, 573 (8) [M- (hPhbztz) r.
Solubility: soluble in dimethylsulfoxide; poorly soluble in chloroform, acetone, acetonitrile and methanol, and insoluble in water.
Example 10: Synthesis and characterization of the complex [lr (L2h (pydat)] CI
On a suspension of [I r (dfppy), (~ -CI)], (100 mg, 0.083 mmol) in 8 mL of methanol, the 2,4-diamino ligand, 6- (2-pyridyl) -1 is added, 3,5-triazine (32 mg, 0.170 mmol) and 6.4
5 mL dichloromethane. The mixture is brought to 60 oC for 24 hours under constant stirring in a nitrogen atmosphere. The mixture is brought to almost dryness in vacuo and the precipitate formed is filtered by washing it with two 8 mL portions of hexane. The product is dried under vacuum for 4 hours at 65 oC. Yield 63%
10 Molecular weight: 796.21 glmol Elemental analysis (%) calculated for C30H2QCIF4IrNs · 2.5H20: C, 42.85; H, 3.00; N, 13.32. Found: C, 42.75; H, 3.02; N, 13.67.
'H NMR (400 MHz, DMSO-dquot; 25 oC): O 8.59 (d, J = 7.6 Hz, 1 H), 8.45 (d, J = 5.6 Hz, 15 1H), 8.38 -8.26 (m, 2H) , 8.14 -8.04 (m, 2H), 7.99 (s, 1 H), 7.89 (d, J = 11.3 Hz, 2H, NH), 7.81 -7.74 (m, 2H), 7.60 (d, J = 5.9 Hz, 1 H), 7.38 (t, J = 6.5 Hz, 1 H), 7.33 (t, J =
7.0 Hz, 1 H), 7.02 -6.91 (m, 2H), 5.63 (dd, J = 8.2, 2.2 Hz, 1 H), 5.45 (dd, J = 8.4, 2.2 Hz, 1 H), 4.97 (s, 1 H, NH). 19F NMR (376 MHz, DMSO-dquot; 25 oC): 0-105.95 (q, J = 9.3 Hz, 1F), -106.34 (q, J = 9.5
20 Hz, 1 F), -107.88 (t, J = 12.0 Hz, 1 F), -108.79 (t, J = 11.7 Hz, 1 F). MS (FAB '): miz (%) = 760 [M-CI]'. 573 [M-CI- (pydatz)) '. Solubility: soluble in acetonitrile and dimethylsulfoxide; little soluble in chloroform, acetone and methanol, and insoluble in water.
Example 11: Synthesis and characterization of the complex [lr (L'MaPhbzim)] CI On a suspension of [lr (bzqh (~ -CI)] 2 (100 mg. 0.085 mmol) in 8 mL of methanol ligand 2 is added - (2-Aminophenyl) -1H-benzimidazole (37.6 mg. 0.180 mmol) and 6.4 mL
5 dichloromethane. The mixture is brought to 60 oC for 24 hours under constant stirring in a nitrogen atmosphere. The mixture is brought to almost dryness in vacuo and the precipitate formed is filtered by washing it with two 8 mL portions of hexane. The product is dried under vacuum for 4 hours at 65 oC. Yield 79% Molecular Weight: 793.35 glmol
10 Elementary analysis (%) pending analysis.
1H NMR (400 MHz, DMSO-d (i, 25 oC): pending assignment.
MS (FAB-): miz ('lo) = 758 (33) [M-CIf. 549 (38) [M-CI- (apbzim) r. 210 (24) [apbzimHr.
Solubility: poorly soluble in chloroform, dimethylsulfoxide, acetone, acetonitrile and methanol, and insoluble in water.
Example 12: Synthesis and characterization of the complex [lr (L8h (btzH)] CI
On a suspension of [lr (bzqh (~ -CI)] 2 (100 mg. 0.085 mmol) in 8 mL of methanol
the thiabendazole ligand (36.2 mg, 0.1 80 mmol) and 6.4 mL of dichloromethane are added. The mixture is brought to 60 oC for 24 hours under constant stirring in an atmosphere of
nitrogen. The mixture is brought to almost dryness in vacuo and the precipitate formed is filtered by washing it with two 8 mL portions of hexane. The product is dried under vacuum for 4 hours at 65 oC. Yield 54%.
5 Molecular Weight: 785. 10 g / molElemental analysis (%) calculated for C) 6H23CllrNsS'2CH2C12: C, 47.78; H, 2.85; N,
7.33; S. 3.36; Found: C. 47.30; H. 3.02; N. 7.38; S. 3.31.
'H NMR (400 MHz, CDCIquot; 25 oC): O 15.45 (s. 1H. NH). 9.97 (s. 1H. H '). 8.17 (d. J =
4 4 '6
10 8.1 Hz. 1H. H). 8. 11 (d. J = 8.0 Hz. 1H. H). 8.04 (d. J = 5.4 Hz. 1H. H). 7.98 (s. 1H. Hb), 7.84 (d, J = 5.4 Hz, 1 H, H '). 7.81 -7.72 (m. 2H. H13 • H13 ·). 7.70 (d. J = 8.3 Hz. 1 H. Hi). 7.62 (d. J = 8.8 Hz. 1 H. H14). 7.52 (d. J = 8.8 Hz. 1H. H'4). 7.43 (d. J = 7.9 Hz. 1 H. Hquot;). 7.38 (d. J = 7.9 Hz. 1H. Hquot;). 7.31 (t. J = 8.0 Hz. 1H. H '). 7.26 (t. J = 7.7Hz. 1H. H '). 7.15 -7.03 (m. 3H. Hi. Hquot;. HU). 6.74 (l. J = 7.8 Hz. 1H. Hk). 6.44 (d. J = 7.3 Hz.
15 1H. H12). 6.40 (d. J = 7.2 Hz. 1 H. H12). 5.96 (d. J = 8.3 Hz. 1 H. H ').
MS (FAB '): miz (%) = 750 (100) (M-CIf. 549 (53) (M-CI-lbzHJ'. 202 (22) (lbzH, J '
Solubility: soluble in dimethylsulfoxide and acetonitrile; poorly soluble in chloroform.
acetone and methanol, and insoluble in water.
Example 13: Synthesis and characterization of the complex (Ir (L 8h (pydat)) CI
lc,
On a suspension of [Ir (bzq), (~ -CI)], (100 mg. 0.085 mmol) in 8 mL of melanol, the 2,4-diamino-6- (2-pyridyl) -1 ligand is added, 3,5-triazine (33.8 mg, 0.180 mmol) and 6.4 mL of dichloromethane. The mixture is brought to 60 oC for 24 hours under constant stirring in a nitrogen atmosphere. The mixture is brought to almost dryness under vacuum and the
The precipitate formed is filtered by washing it with two 8 mL portions of hexane. The product is dried under vacuum for 4 hours at 65 oC. 68% yield.
Molecular weight: 772.29 glmol.5 Elemental analysis (%) calculated for C34H24CllrN8 · 3.5H20: C, 48.89; H, 3.74; N, 13.41. Found: C. 48.94; H. 3.91; N. 13.48.
'H NMR (400 MHz, DMSO-dquot; 25 oC): pending resolution. MS (FAB '): miz (%) = 737 (18) [M-Clr. 549 (28) [M-CI- (pydatz) t. 189 (67) [ydatzHr. Solubility: soluble in acetonitrile and dimethylsulfoxide; little soluble in chloroform, acetone and methanol, and insoluble in water.
Example 14: Synthesis and characterization of the complex [lr (Llh (pybzlm)] CI
fifteen '· . quot;
. ' OR
8'2 6'1 k
n '' N quot;, ~.
7 '~) = (; J
'quot; I e /// I ~~ i
'h •• I, quot; quot;' \ ~ N-H h
12 ../ r ........... g
I
'OC'quot; I ~ N '~'.
NI h ~ I
quot; , 9 8'0 ', quot;
,
On a solution of [lr, CI, (tpy),) (0 .1 g, 0.086 mmol). ligand 2- (2 is added
20 pyridyl) benzimidazole (0.037 9. 0.0189 mmol) together with 8 mL of dichloromethane and 10 mL of distilled methanol. Everything is left at reflux for 24 h at 60 oC. The solution is taken to dryness. The solid obtained is washed with diethyl ether and filtered with celite. Finally it dries under vacuum. A yellow-green solid is obtained. Yield: 65.84%.
Molecular weight: 759.31 glmol.Elemental analysis (%) calculated for C36H29NsCllr '1, 6H20: C 54.86; H 4.12; N 8.89;Found: C 54.85; H 4.17; N 8.66
'H NMR (400 MHz, DMSO-dquot; 25 oC) or = 15.27 (s, lH), 8.79 (d, J = 8.0 Hz, lH), 8.32 (t, J = 7.9 Hz. 1 H). 8. 18 (d, J = 8.2 Hz, 1H), 8.12 (d, J = 8.2 Hz, 1 H), 7.90 -7.77 (m. 5H),
7.73 (d. J = 8.2 Hz, lH), 7.70-7.60 (m, 3H). 7.35 (t, J = 7.8 Hz, lH). 7.12 -7.04 (m, 2H), 7.01 (t. J = 7.8 Hz, 1H), 6.90 (d, J = 7.9 Hz. 1 H), 6.85 (d. J = 7.6 Hz. 1 H). 6.17 (d.
5 J = 8.4 Hz. LH). 6.12 (s, lH), 6.05 (s. LH). 2.09 (s, 3H), 2.08 (s. 3H) ppm. quot; c {'H} NMR (101 MHz, DMSO-dquot; 25 oC) or = 167.11 (s, 1e). 166.97 (s, 1C). 153.34 (s, 1C). 151.42 (s, 1C). 150.20 (s, 1C). 149.21 (s, l e). 148.93 (s, 1e). 147.37 (s, 1e).
141.97 (s. L e), 141.65 (s. L e), 139.90 (s. L e), 139.77 (s. 1e), 139.48 (s. 1e), 138.80 (s, 1C). 138.39 (s, 1C). 138.18 (s, 1C). 134.59 (s, l e). 132.44 (s, 1e). 131.77 (s, 1e).
10 128.53 (s. Le), 125.37 (s, le), 124.98 (s. Le), 124.57 (s, 1e), 124.51 (s. 1e), 124.30 (s, l e), 123.30 (s, l e). 123.17 (s, l e), 123.14 (s, l e), 122.97 (s, l e), 119.41 (s, 1e),
119.12 (s. L e), 116.57 (s. 1 e), 113.81 (s. L e), 21.52 (s. 1 e). 21.51 (s. L e) ppm. FT-IR (ATR, cmquot;): 3300 (w, v N-H), 2946 (w, V.eH), 1603 (s, Ve ~ e le-N). 1473 (s. Ve ~ N). 1447 (s), 773 (w. Óe.el. 751 (s, ÓCHoop).
15 MS (FAB '): miz (%) = 723.76 (100) ([M-el]'). 528.78 (50) ([M-Cl-L, J ') Molar conductivity (CH 3CN): 22 8 cm2 mol. Solubility: soluble in DMSO, chloroform and dichloromethane and partially soluble in acetone.
20 Example 15: Synthesis and characterization of the complex (Ir (Llh (pyNMebzlm)] CI
On a solution of [lr, el, (tpy).) (0 .1 g, 0.086 mmol), ligand 2- (225 pyridyl) N-methylbenzimidazole (0.0396 g, 0.189 mmol) is added together with 8 mL of dichloromethane and
10 mL of distilled methanol.
Everything is left at reflux for 24 h at 50 oC. The solution is taken to dryness. The solid obtained is washed with diethyl ether and filtered with celite. Finally it dries under vacuum,
A yellow-orange solid is obtained. Yield: 78.4%.
Molecular weight: 773,344 glmol Elemental analysis (%) calculated for C37H3, NsCllr-5H20: C 50.42; H 4.92; N 7.95; Found: C 50.49: H 4.83: N 7.68
'H NMR (400 MHz, DMSO-dquot; 25 oC) or = 8.77 (d, J = 8.3 Hz, 1 H, H'), 8.28 (1, J = 7.9 Hz, 1H, H '), 8.19 (d , J = 8.0 Hz, 1H, H '), 8.12 (d, J = 8.1 Hz, 1H, H'), 7.97 -7.91 (m, 2H, Hb.,), 7.87 -7.78 (m, 4H, Hquot; quot; ·, ·,), 7.71 (1, J = 7.1 Hz, 1H, H '), 7.65 (d, J = 5.3 Hz, 1H, H'), 7.59 (d, J = 5.6 Hz, 1H, Hquot ;), 7.42 (1, J = 7.7 Hz, 1H, Hk), 7. 12 -7.00 (m, 3H, H4.4 ',,), 6.90 (d, J = 7.6 Hz, 1H, Hquot;), 6.85 (d, J = 7.9 Hz, 1H, Hquot; '), 6.22 (d, J = 8.3 Hz, 1H, Hm), 6.08 (s, 1 H, H12), 6.01 (s, 1 H, H12), 4.45 (s, 3H, Hh), 2.08 (s, 6H, Hquot; '' ') ppm. quot; e eH} NMR (101 MHz, DMSO-dquot; 25 oC) or = 167.08 (s, 1C), 166 .90 (s, 1C), 152 .73 (s, 1C), 151.88 (s, 1C), 150.87 (s, 1C), 149.35 (s, 1C), 148.94 (s, 1C), 147.79 (s, 1C), 146.94 (s, 1C), 141.86 (s, 1C), 141.52 (s, 1C), 139.52 (s, 1C), 139.47 (s, 1C), 138.84
(s, 1C), 138.65 (s, 1C), 138.37 (s, 1C), 138.15 (s, 1C), 136.51 (s, 1C), 132.34 (s, 1C),
131.57 (s, 1C), 128.40 (s, 1C), 126.09 (s, 1C), 125.32 (s, 1C), 125.02 (s, 1C), 124.84 (s, 1C), 123.16 (s, 1C) , 123.07 (s, 1C), 122.97 (s, 1C), 119.44 (s, 1C), 119.11 (s, 1C), 116.84 (s, 1C), 112.51 (s, 1C), 48.58 (s, 1C), 25.48 (s, 1C), 21.53 (s, 1C) ppm,
FT-IR (ATR, cmquot;): 2963 (w, V.eH), 1604 (s, Ve_el e.N), 1478 (s, Ve_N), 1427 (w, ÓeH3quot; im),
1350 (w, ÓeHquot; im), 780 (w, óe.e), 742 (s, ÓeHoop),MS (FAB '): miz (%) = 737.78 (100) ([M-Cln, 528.75 (100) ([M-CI-L,]')
Molar conductivity (CH3CN): 91.5 S · cm2 / mol.Solubility: soluble in DMSO, chloroform and dichloromethane and partially soluble inacetone.
Example 16: Synthesis and characterization of the complex [lr (L3h (thbzol)] CI
On a solution of [lr, CI, (lpy), l (0.1 g, 0.086 mmol), the ligand is added
5 thiabendazole (0.0381 g, 0.0189 mmol) together with a dichloromethane / methanol mixture
(4: 5 18 mL). Everything is left at reflux for 24 h at 60 oC. The solution is taken to dryness. The solid obtained is washed with diethyl ether and filtered with celite. Finally dried under vacuum, a yellow solid is obtained. Yield: 72.25%
10 Molecular Weight: 725.40 glmol
Elemental analysis (%) calculated for CJ4Hz7NsSCllr · 3HzO: C 49.84; H 4.06; N 8.55
: Found: C 50.11: H 3.95: N 8.51
'H NMR (400 MHz, DMSO-dquot; 25 oC) or = 15.54 (s, 1H, H'), 9.21 (s, 1H, H '), 8.49 (s, 15 1H, Hb), 8.18 (d, J = 8.2 Hz, 1H, H '), 8.11 (d, J = 8.3 Hz, 1H, H' '), 7.87 (1, J = 7.8 Hz,
1H, H '), 7.83 -7.76 (m, 3H, Hquot; ·, ·, ·), 7.74 -7.69 (m, 2H, H3 •'), 7.67 (d, J = 8.2 Hz, 1H, H ') , 7.28 (1, J = 7.7 Hz, 1 H, Hi), 7.1 5 -7.04 (m, 2H, H'.4 '), 6.96 (1, J = 7.8 Hz, 1 H, Hquot;), 6.88 (d, J = 7.9 Hz, 1 H, Hquot;), 6.82 (d, J = 8.0 Hz, 1 H, Hquot; '), 6.15 (s, 1 H, Hquot;'), 6.12 (d, J
= 8.2 Hz, 1H, H '), 6.09 (s, 1H, Hquot;), 2.07 (s, 3H, Hquot;), 2.06 (s, 3H, Hquot;') ppm. 20 .oc {'H} NMR (101 MHz, DMSO-dquot; 25 oC) or = 167.14 (s, 1C, C'), 167.05 (s, 1C, c ''),
159.07 (s, 1C, Cb), 149.15 (s, 1C, C '). 148.72 (s, 1C, C3 '), 148 .48 (s, 1C, Cquot;'), 147.23 (s, 1 C, Cquot;), 144.53 (s, 1C, C '), 142.05 (s, 1 C , C '), 141.93 (s, 1 C, c' '), 139.45 (s, 1 C, Cm), 139.05 (s, 1C, Cquot;), 138.73 (s, 1C, C'), 138.34 (s , 1C, C '), 138.18 (s, 1C, c''gt ;. 134.27 (s, 1C, COl, 132.41 (s, 1C, cquot;), 132.12 (s, 1C, cquot; '), 125.76 (s, 1C, c'), 124.76
25 (s, 1C, c '), 124.73 (s, 1C, c' '), 124.55 (s, 1C, Ci), 123.83 (s, 1C, cquot;), 123.22 (s, 1C, C'), 123.11 (s, 1 C, c ''), 122.98 (s, 1 C, Cquot;), 122.86 (s, 1 C, cquot; '), 119.36 (s, 1 C, C'),
119.02 (s, 1C, c ''), 116.34 (s, 1C, C '), 113.39 (s, 1C, C'), 21.50 (s, 1C, Cquot;), 21.48 (s, 1C, cquot; ' ) ppm.
FT-IR (ATR, cmquot;): 3063 (w, VeoeH), 1605 (s, Veoe I e.N), 1476 (s, VeoN), 772 (w, óe.c),751 (s, ÓeHquot ;,).MS (FAB '): miz (%) = 729.76 (100) ([M-CI]'), 528.80 (60) ([M-CI-L,] ')Molar conductivity (CH3CN): 18.8 S · cm2 / mol.Solubility: soluble in DMSQ, chloroform and dichloromethane and partially soluble inacetone.
Example 17: Synthesis and characterization of the complex (Ir (Llh (aphbzlm)] CI
On a solution of [lr, CI, (tpy),) (0.1 g, 0.086 mmol), the ligand 2- (2aminophenyl) -benzimidazole (0.398 g, 0.189 mmol) is added together with 8 mL of dichloromethane and 10
mL of distilled methanol.
15 Everything is left at reflux for 24 hours at 60 ° C. Everything is left at reflux for 24 h at 60 oC. The solution obtained is taken to dryness. The solid obtained is washed with diethyl ether and filtered with celite. Finally, it is dried under vacuum and a yellow solid is obtained. Yield: 75.93%.
20 Molecular weight: 773,345 g / mol Elemental analysis (%) calculated for CJ7Hquot; N, Cllr'2.5H, O: C 54.3; H 4.43; N 8.56; Found: e 54.43; H 4.46; N 8.29
'H NMR (400 MHz, DMSQ-dquot; 25 oC) or = 14.21 (s, 1 H), 8.69 (d, J = 5.9, 1.4 Hz, 1 H),
25 8.24 (d, J = 8.3, 1.4 Hz, lH), 7.95 -7.89 (m, 2H), 7.88 -7.83 (m, 2H), 7.77 (d, J = 8.0 Hz, lH), 7.67 (1, J = 7.7 Hz, lH), 7.61 (d, J = 8.0 Hz, lH), 7.56 (d, J = 8.1 Hz, 1H), 7.52 (d, J = 10.7 Hz, lH), 7.22 (t, J = 7.3 Hz, lH), 7.19 -7.13 (m, 2H), 7.10 (t, J = 8.2 Hz, lH), 6.78 (m, 2H), 6.75 -6.64 (m, 3H), 6.56 (d, J = 10.7 Hz , lH), 6.41 (d, J = 8.4 Hz, 1 H), 5.96 (s, 1 H), 5.67 (s, 1 H), 1.97 (s, 3H), 1.88 (s, 3H) ppm.
quot; e eH} NMR (101 MHz, DMSO-dquot; 25 oC) ~ = 168.31 (s, lC), 166.74 (s, lC), 150.39 (s, lC), 149.93 (s, lC), 149.83 (s, lC ), 149.36 (s, lC), 148.53 (s, lC), 142.69 (s, l C), 142.50 (s, l C), 142.17 (s, lC), 142.07 (s, lC), 138.18 (s, lC), 138.12 (s, lC), 137.54 (s, lC), 134.06 (s, lC), 132.45 (s, lC), 131.91 (s, l C), 131.35 (s, l C), 130.08 (s , l C),
5 124.61 (s, l C), 124.15 (s, lC), 123.46 (s, lC), 122.65 (s, lC), 122.51 (s, lC), 122.25(s, lC), 122.05 (s, lC), 121.92 (s, lC), 121 .85 (s, l C), 121.19 (s, l C), 119.28 (s, l C),
118.23 (s, lC), 117.12 (s, lC), 112.35 (s, lC), 64.94 (s, l e), 48.61 (s, lC), 21 .60 (s,l C), 21.36 (s, l C) ppm.FT-IR (ATR, cm- '): 3396 (w, v N-H), 3010 (w, v C ~ CH), 1605 (s, vc ~ cl CoN), 1476 (s, VC ~ N),
10 770 (w, ~ c-c), 748 (s, ~ c_). MS (FAB '): miz (%) = 737.75 (100) ([M-Cln, 528.72 (82) ([M-CI-L5]') Molar conductivity (CH 3CN): 32.4 S · cm2 / mol Solubility: soluble in DMSQ, chloroform and dichloromethane and partially soluble in acetone.
Example 18: Synthesis and characterization of the complex [lr (Llh (pydaT}] CI
.
S ' . '·
lO '2
116 m.
OR
'N H2N k J I 13' 11 'Oe 7' I rN ~ i NH
2 Me 12 '¡¡¡quot; ,, Ir quot; quot ;,' '' '6 \ - yN h
\ N g. I Oquot; bquot; Iquot; quot; 'quot;' N '~,
IJ I b e
"ON ~
6 d
,,
S
On a solution of [lr, CI, (IPY) 4) (0.1 g, 0.086 mmol), the ligand 2,4diamino-6- (2-pyridyl) -1, 3,5 triazine (0.356 g, 0.189 mmol) is added ) with 8 mL of dichloromethane
20 and 10 mL of distilled methanol. Everything is left at reflux for 24 h at 60 oC. The solution obtained is taken to dryness. The solid obtained is washed with diethyl ether and filtered with celite. Finally it is dried under vacuum and very little yellow solid is achieved. Yield: 40.42%.
25 Molecular weight: 752,286 glmol Elemental analysis (%) calculated for Cquot; Hquot; N, Cllr'2.3H, O: C 48.42; H 4.14; N 14,12; Found: C 48.63; H 4.18; N 13.81
'H NMR (400 MHz, DMSO-dquot; 25 oC) or = 8.55 (d, J = 8.1, Hz, 1 H, H'), 8.29 -8.24 (m, 3H, Hquot; quot; ·,), 8.20 (d, J = 8.2 Hz, 1H, H '), 8.02 -7.90 (m, 2H, Hquot; A), 7.88 -7.84 (m, 2H, Hquot; quot;), 7.82 -7.71 (m, 4H, Hquot ; quot; quot; '), 7.69 (d, J = 5.2 Hz, 1H, Hb), 7.50 (d, J = 5.8 Hz, 1H,
5 H '), 7.26 (t, J = 8.1 Hz, 1H, H'), 7.20 (t, J = 7.8 Hz, 1H, H '), 6.84-6.82 (m, 2H, Hquot;' ''), 5.99 (s, 1 H, Hquot; '), 5.80 (s, 1 H, Hquot;), 5.33 (s, 1 H, H'), 2.03 (s, 3H, Hquot;), 2.02 (s, 3H, Hquot;) ppm. quot; c {'H} NMR (101 MHz, DMSO-dquot; 25 oC) or = 170.51 (s, 1C, C'), 166.65 (s, 1C, c '),
166.42 (s, 1C, C '), 165.19 (s, 1C, C'), 164.91 (s, 1C, Ci), 153.94 (s, 1C, CI), 150.22 (s, 10 1C, C '), 149 .25 (s, 1C, Cb), 148.69 (s, 1C, c ''), 148 .64 (s, 1C, C7), 147.56 (s, 1C, C '),
142.16 (s, 1C, c '), 141.10 (s, 1C, C'), 139.94 (s, 1C, Cquot; '), 139.82 (s, 1C, Cquot;), 139.58 (s, 1 C, C' ), 138.71 (s, 1C, C '), 138.67 (s, 1 C, C'), 132.18 (s, 1 C, cquot;), 130.85 (s, 1 C, Cquot;), 130.66 (s, 1C , C '), 127.18 (s, 1C, C'), 125.54 (s, 1C, c '), 125.05 (s, 1C, C'), 123.76 (s, 1C, C '), 123.68 (s, 1C, C'), 123.67 (s, 1C, Cquot;), 123.61 (s, 1C, Cquot;), 119.78
15 (s, 1C, C '), 119.67 (s, 1C, C'), 21.52 (s, 1C, Cquot;), 21.46 (s, 1C, cquot;) ppm. FT-IR (ATR, cm- '): 3361 (w, v NH), 3026 (w, Ve_eH), 1625 (s, Ve_el eN), 1477 (s, Ve_N), 778 (w, oe-e), 764 (s, ÓeHoop). MS (FAB '): miz (' lo) = 716.67 (100) ((M-Cl] '). 528.72 (20) ((M-CI-L.]')
Molar conductivity (CH 3CN): 91.4 S · cm2 / mol.
20 Solubility: soluble in DMSQ, chloroform and dichloromethane and partially soluble in acetone.
Example 19: Synthesis and characterization of the complex [lr (L3h (hphbzlm)]
.
On a solution of [Ir, el, (tpy),) (0 .1 g, 0.086 mmol), the ligand 2- (2-hydroxyphene) -benzimidazole (0.398 g, 0.189 mmol) is added next to the Na, eO salt , (0.0365 g, 0.344
mmol) and a mixture of ethoxyethanol / water (1: 1 20 mL) previously deoxygenated.Everything is left at reflux for 24 h at 110 oC. Filter and finish evaporatingleading to dryness with the help of a vacuum trap. The solid is washed with diethyl etherand is filtered 3 times to ensure that it is completely free of impurities.It is then dried under vacuum for a couple of hours, and finally a solid is obtainedyellow. Yield: 64.1%.
Molecular Weight: 737.87 g / molElemental analysis (%) calculated for C37H29N40Ir · 4,5H20: C 54.27; H 4.68; N 6.84;
Found: e 54.83: H 4.18: N 6.38
'H NMR (400 MHz, DMSO-dquot; 25 oC) 6 = 8.78 (d, J = 5.8 Hz, 1 H), 8.08 -7.94 (m, 3H),
7.80 -7.70 (m, 4H), 7.67 (d, J = 8. 1 Hz, 1 H), 7.57 (d, J = 7.8 Hz, 1 H), 7.37 (d, J = 8.0Hz, 1H), 7.14 (t, J = 6.6 Hz, 1H), 7.04 -6.95 (m, 3H), 6.71 -6.64 (m, 1H), 6.67 (d, J =
7.5 Hz, 1 H), 6.61 (d, J = 7.8 Hz, 1 H), 6.54 (t, J = 7.8 Hz, 1 H), 6.38 -6.32 (m, 2H), 6. 18(d, J = 8.4 Hz, 1H), 6.11 (s, 1 H), 5.77 (s, 1 H), 1.99 (s, 3H), 1.97 (s, 3H) ppm.13C {'H) NMR (101 MHz, DMSO-dquot; 25 oC) 6 = 167.93 (s, 1e), 167.49 (s, 1C), 166.30(s, 1C), 153.79 (s, 1C), 151.34 (s, 1e), 149.43 (s, 1C), 149.24 (s, 1e), 147.88 (s, 1e),
142.89 (s, 1e), 142.43 (s, 1e), 142.27 (s, 1C), 137.71 (s, 1C), 137.35 (s, 1C), 137.00(s, 1C), 136.88 (s, 1C), 135.03 (s, 1e), 133.59 (s, 1C), 131.97 (s, 1e), 131.22 (s, 1e),
128.40 (s, 1e), 124.59 (s, 1e), 123.66 (s, 1 e), 123.18 (s, 1 e), 121.95 (s, 1 e), 121.63(s, 1 e), 121.49 (s, 1 e), 121.03 (s, 1 e), 120.86 (s, 1C), 120.79 (s, 1e), 118.46 (s, 1 e),
118.07 (s, 1e), 117.31 (s, 1e), 114.91 (s, 1C), 112.48 (s, 1C), 111.32 (s, 1e), 21.48 (s,1e), 21.43 (s, 1 C) ppm.FT-tR (ATR, cm- '): 1460 (s, VC ~ N), 770 (w, Cc-e) _MS (FAB-): miz ('lo) = 738_06 (25) ([Mn, 529_07 (100) ([M-L, f)
Solubility: soluble in DMSQ, chloroform and dichloromethane and partially soluble in acetone.
Example 20: Synthesis and characterization of the complex [lr (L3h (hphbzTz)]
"
13 '
I
I
On a solution of [lr, CI, (tpy),] (0.1 g, 0.086 mmol), ligand 2 (2-hydroxyphenyl) -benzothiazole (0.043 g, 0.189 mmol) is added next to the Na, CO salt (0.0365 g , 0.344 mmol) and a mixture of ethoxyethanol / water (1: 1 20 mL) previously deoxygenated.
5 Everything is left at reflux for 24 h at 110 oC. It is filtered and evaporated, leading to dryness with the aid of a vacuum trap-N 2. The solid is washed with diethyl ether and filtered 3 times to ensure that it is completely free of impurities. It is then dried under vacuum for a couple of hours, and finally an orange-reddish solid is obtained. Yield: 56.22%.
10 Molecular weight: 754.92 g / mol Elemental analysis (%) calculated for C37H28N30Slr · H20: e 57.5; H 3.91; N, 5.44; Found: C 57.55; H 3.77; N 5.33.
15 'H NMR (400 MHz, COCIquot; 25 oC) or = 9.09 (d, J = 5.7 Hz, lH, H'), 8.20 (d, J = 5.8 Hz, lH, H '', 7.84 (d, J = 7.9 Hz, 1H, Hb), 7.72 -7.57 (m, 4H, H '··· A.), 7.57 -7.43 (m, 2H, Hquot; ·,), 7.39 (d, J = 7.8 Hz , lH, H '), 7.10 (t, J = 7.7 Hz, lH, H'), 7.04 -6.92 (m, 3H, HmM), 6.84 (t, J = 8.6 Hz, 1 H, H '), 6.76 -6.61 (m, 3H, Hquot; quot; '' '), 6.48 (d, J = 8.6 Hz, 1 H, Hi), 6.37 (t, J = 8.1 Hz, lH, H'), 6.28 (s, lH, Hquot;), 5.83 (s, lH, Hquot;), 2.04 (s, 3H, Hquot;),
20 2.03 (s, 3H, Hquot;) ppm. quot; c {'H} NMR (101 MHz, OMSO-dquot; 25 oC) or = 169.13 (s, lC, C), 168.74 (s, lC, C),
168.67 (s, lC, C), 168.35 (s, lC, C), 154.29 (s, lC, e '), 150.56 (s, lC, C'), 150.27 (s, lC, C), 149.06 (s , lC, e), 148.51 (s, le, C), 142.31 (s, lC, C), 141.60 (s, le, C), 139.23 (s, lC, C), 139.17 (s, l C, C), 136.68 (s, l C, e '), 136.44 (s, l C, c``, 134.55
25 (s, lC, c`;), 133.38 (s, le, Cm), 132.54 (s, lC, C), 132.00 (s, le, Cquot;), 130.84 (s, lC, C '), 126.12 (s, lC, C '), 124.80 (s, 1 C, C'), 124.47 (s, lC, C '), 124.37 (s, le, C'), 123.46 (s, lC, Cquot;), 122.80 (s, lC, C '), 122.73 (s, lC, c'), 121.53 (s, lC, c '), 121.41
(s, 1C, C), 120.95 (s, 1C, C5), 120.82 (s, 1C, Cquot;), 120.72 (s, 1C, Cquot; '), 118.12 (s, 1C, C'), 117.99 ( s, 1C, C '), 114.43 (s, 1C, C'), 22.14 (s, 1C, Cquot;), 21.84 (s, 1C, cquot;) ppm
MS (FAB-): miz (%) = 754.63 (90) ([Mn, 528.70 (100) ([M-Lorgt;
5 Molar conductivity (CH3CN): 2.6 S · cm2, mol.Solubility: soluble in DMSQ, chloroform and dichloromethane and partially soluble inacetone.
Example 21: Synthesis and characterization of the complex [lr (L 6h (PyBzlm}] CI
In a Schtenk flask a mixture of (Ir, (L ') 4] (0.1000 g, 0.0782 mol), pyridylbenzimidazole (32. 146 mg 164.67 mmol), 5 mL of methanol and 4 mL CH, CI is prepared and prepared
15 heat to reflux with stirring at 60 ° C overnight. Reaction mixture
acquires an intense red color. It is evaporated to dryness and the residue obtained is
wash with n-hexane. The solid is filtered and dried in vacuo. An orange solid is obtained.
Yield: 74%.
20 Molecular weight: 831.3976 glmol Elemental analysis (%) calculated for Cquot; Hquot;, N5IrCI '(CH, CI,) or,' (H, Oj ,,: C 55.01; H 3.78; N 7.51; Found: C 55.10; H 3.75; N 7.42.
'H NMR (400 MHz, COCh, 25 oC) or = 16.22 (s, 1H, HN.quot;), 9.75 (d, J = 8.1 Hz, 1H, H'),
25 8.98-8.87 (m, 2H, H '' '), 8.27 (dd, J = 7.9, 4.9 Hz, 3H, Hquot;' ''), 8.05 (t, 1H, H '), 7.92 (d,
J = 8.3 Hz, 1H, H '), 7.89 -7.82 (m, 2H, Hquot;'), 7.74 (m, J = 11.7, 6.4, 3.4 Hz, 4H, H55
. ·.,.,), 7.66 (d, J = 4.8 Hz, 1H, H '), 7.57 (d, J = 6.4 Hz, 1H, Hquot;), 7.36 (d, J = 6.4 Hz, 1H, Hquot; '), 7.29 -7.22 (m, 4H, b, H9.9', iI, 7.18 (t, J = 7.6 Hz, 1H, H15 '), 7.1 1 (t, J = 7.6 Hz,
1 H, H15), 6.89 (t, J = 7.4 Hz, 3H, Hk.quot;. ,, '), 6.44 (d, J = 7.6 Hz, 1 H, H13'), 6.34 (d, J = 7.7
Hz, 1 H, H13), 5.91 (d, J = 8.4 Hz, 1 H, H ').13C ('H) NMR (101 MHz, CDCIquot; 25 oC) 00 169.50 (5, 1C, C'), 169.26 (5, 1C, c``,
5 155.01 (5, 1C, Cquot;), 152.95 (5, 1C, C '), 150.21 (5, 1C, cquot;'), 148.78 (5, 1C, C '), 146.24 (5,1C, C '), 146.16 (5, 1C, Cquot;), 141.32 (5, 1C, cquot;'), 140.42 (5, 1C, Cquot;), 140.03 (5, 1C, cquot; '),139.53 (5, 1 C, C '), 137.ü7, 136.89, 135.28 (5, 1 C, Cquot;), 133.20 (5, 1 C, C13), 132.48 (s, 1 C,
C13
'), 131.64, 131.55, 130.86, 130.71, 130.48, 130.05, 128.67, 128.60, 127.66, 127.48,
. k 127.21, 127.12,126.96, 126.63, 126.37, 126.35, 125.50 (s, 1C, C '), 124.54 (s, 1C, C),
I.
10 122.16, 122.04, 121.64,121.50, 117.12 (s, 1C, C), 114.92 (s, 1C, C '), 77.37, 31.08_ FT-IR (cm-'): 3033 (w, Ve_eH), 1604 ( m, ve_e), 1048 (m, Ve_N), 628 (s, Oc_e), 734 (vs,
iCHoop)
MS (FAB +): m / z (%) = 601 ([Ir (piq), - H ']), 796 ([M-CI1)
Molar conductivity (CH 3CN): 24.15 S · cm2 · mor1.
Solubility: soluble in ethyl ether, chloroform, methanol and acetone, partially soluble in acetonitrile and insoluble in hexane.
Example 22: Synthesis and characterization of the complex [lr (L 6h (tbz)] CI
A mixture of [Ir, (l '),) (0.075 g, 58.94 mmol) is prepared in a Schlenk flask,
Thiabendazole (24.99 mg 124.17 mmol), 5 mL of methanol and 4 mL CH 2CI2 and heated to reflux with stirring at 60 ° C overnight. The reaction mixture acquires an intense red color. It is evaporated to dryness and the residue obtained is washed with 2
25 fractions of 5 mL of n-hexane. The solid is filtered and dried in vacuo. An orange solid is obtained.
Molecular weight: 837.4058 g / mol Elemental analysis (%) calculated for C4oH27NslrSCI '(CH30H)' (H20): C 55.49; H 3.45; N 7.89 S 3.61; Found: C 55.49; H 3.96; N 7.52; S 3.28.
'H NMR (400 MHz, COCIquot; 25 oC) or = 15.76 (s. LH. H'). 10.16 (s. LH, H '). 8.93 (m. 2H. H '' '), 8.26 (d, J = 8.1 Hz, 2H, H16.16 ·), 7.94 (s, 1 H, Hb), 7.88 (m, 2H, Hquot;'), 7.76 (m. J =
14.1,9.4,6.5 Hz, 6H, H '·' ·· '·' ·· 1O · 1O), 7.39 (d, J = 6.4 Hz, 1 H, H '), 7.29 (d, J = 6.0 Hz, 2H,
Hquot; '), 7.23 (1, J = 7.6 Hz, 1 H, Hh), 7.20 (1, J = 5.0 Hz, 1 H, H15), 7.09 (1, J = 7.7 Hz, 1 H, H15
). 6.88 (dd. J = 14.1. 7.1 Hz. 3H. Hquot; · quot; ·· i). 6.46 (d. J = 7.5 Hz. 1 H. Hquot;). 6.39 (d. J =
10 7.5 Hz. 1 H. Hquot; ). 5.90 (d. J = 8.3 Hz. LH. Hi). quot; C {'H) NMR (101 MHz, COCIquot; 25 oC) or = 169.44, 169.20, 155.10, 152.04, 150.41, 148.17. 146.51. 146.46. 146.27 (s. LC. C '). 141.52. 140.31 (s. LC. C '). 139.57. 137.11.
136.95. 134.89 (s. LC. C '). 133.12 (s. LC. Cquot;). 132.86 (s. LC. Cquot;). 131.65. 131.53. 130.53 (s. LC. C16). 130.47 (s. LC. C16). 130.44. 130.Q1. 128.69. 128.57. 127.68 (s. LC.
15 C '). 127.48 (s. LC. C '). 127.08 (s. 1C. C '). 126.92 (s. LC. C '·). 126.33. 126.27. 125.67. 124.98 (s, lC. Ch), 124.10, 122.13 (s, lC, C '), 121.99 (s, lC, c'), 121.84 (s, lC, C15), 121.50 (s. IC. C15 '). 117.03 (s. LC. Ci) .114.33.
FT-IR (cmquot;): 3034 (w, VC ~ CH), 1047 (m, VC ~ N), 627 (s, óc ~ cl, 742 (vs, ÓCHoop)MS (FAB +): m / z (%) = 601 ([Ir (piq), - WJ), 802 ([M-CI1)
twenty-one
20 Molar conductivity (CH3CN): 22.9 S · cm · mor
Solubility: soluble in ethanol, chloroform, ethyl ether, acetonitrile and acetone e
insoluble in hexane.
Example 23: Synthesis and characterization of the complex [lr (L 6M2-pydat)] CI
In a Schlenk malraz a mixture of [lr, (L '),) (0.072 g, 57 mmol), 2 is prepared
pyridylbenzimidazole (21.3 mg, 113 mmol), 5 mL of methanol and 4 mL CH2CI2 and
Heat at reflux with stirring at 60 ° C overnight. The reaction mixture acquires an intense red color. It is evaporated to dryness and the residue obtained is washed with 2 fractions of 5 mL of n-hexane. The solid is filtered and dried in vacuo. A red solid is obtained. Yield: Yield: 74%.
Molecular Weight: 824.3658 Glmol'H NMR (400 MHz, COCIquot; 25 oC) or = 8.91 (1, J = 8.8 Hz, 3H, H .... ·'), 8.28 (d, J = 7.9 Hz,1H, H16), 8.24 (d, J = 8.2 Hz, 1 H, H16), 8. 15 (s, 1 H, HN.H), 8.06 (d, J = 6.3 Hz, 2H, HlO,
b), 8.00-7.95 (m, 2H, H7.). 7.91 (s, 1 H, HN.H), 7.78 (m, J = 4.7, 3.3 Hz, 4H, H, ·, ·, 6.6).
10 7.51 (1, J = 5.3 Hz, 2H, Hd ,,), 7.42 -7.33 (m, 2H, Hquot; '), 7.1 7 (d, J = 6.4 Hz, 1 H, HlO') , 7.12 - 7.06 (m, 3H, HN.H, 15.15), 6.83 (q, J = 7.7 Hz, 2H, Hquot; '' '), 6.20 (q, J = 7.6 Hz, 2H,
H13.13), 5.39 (s, 1 H, HN.H).13C {'H} NMR (101 MHz, COCIquot; 25 oC) or = 170.69, 169 .14, 168.64, 165.27, 164.88,
d '10 155.05, 151.88, 149.53 (s, 1C, C), 149.35, 146.01, 145.47, 141.71 (s, 1C, C),
15 139.67 (s, 1C, C10 '), 139.07 (s, 1C, C'), 137.1 9, 137.07, 132.64, 131.89, 131.67, 131.51, 131.36, 131.03, 130.65, 129.76 (s, 1C, C ' ), 128.94 (s, 1C, C '), 128.77, 127.89, 127.57, 127.24, 126.81, 126.55, 126.49, 123.21, 122.62, 122.35, 121.96 (s, 1C, C).
quot;
FT-IR (cmquot;): 3041 (w, VC ~ CH), 1613 (m, vc ~ cl, 1038 (m, VC ~ N), 625 (s, óc ~ cl, 730 (vs,
~ CHOOP)
20 MS (FAB +): m / z (%) = 601 ([Ir (piq), - H ']), 789 ([M-CI1) Molar conductivity (CH3CN): 11 7.37 S'cm2'mor1 Solubility : soluble in methanol, chloroform, ethyl ether, acetonitrile and acetone and insoluble in hexane.

权利要求:
Claims (16)
[1]
1. Ir (lIl) complex of general formula [lr (CAN), (NAO)) or [lr (CAN), (NAN ')] A,
characterized in that A is an anion, each (CAN) is an independent cyclomelated ligand 5 and (NAO) or (NAN ') is an arylazole ligand.
[2]
2. An Ir complex (lIl) according to claim 1, characterized in that said anion A is selected from a halide, hexafluorophosphate, tetrafluoroborate, tetraphenylborate or tosylate;
10 said cyclometalated ligands (CAN) are independently selected from:
H
Hoce
ce) ()
or "I 0
H
and said arylazole ligand (NAO) or (NAN ') is selected from the group consisting of:
20 in which you see OH or NH2, and
X is NH, N-Me, S or O;
quot; ..- N N ~
!! -> -lt; 'X ... J-J
in which X is NH, N-Me, S or O;
N N ----- lt; NH,
C) - lt;
quot; quot; 'quot; N -N
lt;
NH,
where X is N-H, N-CH3 • N-CH2Ph, O or S;
10 in which X is N-CH, Ph, O or S:
:Y
wherein said ligand (NAO) is part of the complex in the deprotonated form.
[3]
3. An Ir complex (llI) according to claim 2, of formula
C N ~
quot; quot ;, 1
5 in which A is a halide.
[4]
4. An Ir complex (lU) according to claim 2, of formula
Oen that A is a halide.
A complex of Ir (llI) according to claim 2, of formula
in which A is a halide.
[6]
6. An Ir complex (II) according to claim 2, of formula
FF
in which A is a halide.
[7]
7. An Ir (I !!) complex according to claim 2, of formula
FF
in which A is a halide.
An Ir complex (lU) according to claim 2, of formula
FF
in which A is a halide.
[9]
9. An Ir complex (II) according to claim 2, of formula
in which A is a halide.
[10]
10. An Ir (I !!) complex according to claim 2, of formula
in which A is a halide.
[11 ]
eleven . An Ir complex (llI) according to claim 2, of formula
in which A is a halide.
[12]
12. An Ir complex (lll) according to claim 2, of formula
II
in which A is a halide. 13. An Ir complex (lU) according to claim 2, of formula
II
in which A is a halide.
[14]
14. An Ir complex (lll) according to claim 2, of formula
M,M,
in which A is a halide.
15. An Ir complex (llI) according to claim 2, of formula
M,M,
in which A is a halide. 16. An Ir complex (lll) according to claim 2, of formula
M,M,
in which A is a halide. A complex of Ir (llI) according to claim 2, of formula
in which A is a halide.
[18]
18. An Ir complex (lll) according to claim 2, of formula
in which A is a halide.
A complex of lr (ll1) according to one of claims 2 to 18. wherein said
Halide is chloride.
[20]
20. An Ir complex (llI) according to claim 2, of formula
FF
[21]
21. An Ir complex (llI) according to claim 2, of formula
FF
[22]
22 A complex of Ir (I !!) according to claim 2, of formula
[23]
2. 3. An Ir complex (II) according to claim 2, of formula

M.
M.

类似技术:

公开号 | 公开日 | 专利标题

CN106459095B|2020-03-10|Metal Organic Framework | yellow phosphor and application thereof in white light emitting device

Williams et al.2008|Light-emitting iridium complexes with tridentate ligands

Whittle et al.2008|A new class of iridium complexes suitable for stepwise incorporation into linear assemblies: Synthesis, electrochemistry, and luminescence

CN101654466B|2013-11-27|Transition metal complexes comprising carbene ligands serving as emitters for organic light-emitting diodes |

JP2014156466A|2014-08-28|Phosphorescent metal complex compound, light emitting element comprising phosphorescent metal complex compound, and method for production of phosphorescent metal complex compound

Alam et al.2014|New ‘aggregation induced emission |’active cyclometalated iridium | based phosphorescent sensors: high sensitivity for mercury | ions

Wang et al.2010|Synthesis, radii dependent self-assembly crystal structures and luminescent properties of rare earth | complexes with a tripodal salicylic derivative

ES2369738T3|2011-12-05|PHOTOEMISOR MATERIAL.

Shao et al.2014|Synthesis and photophysical properties of europium |–β-diketonate complexes applied in LEDs

Tamura et al.2018|Stereospecific synthesis of tris-heteroleptic tris-cyclometalated Iridium | complexes via different heteroleptic halogen-bridged iridium | dimers and their photophysical properties

Gonell et al.2016|Pincer-CNC mononuclear, dinuclear and heterodinuclear Au | and Pt | complexes supported by mono-and poly-N-heterocyclic carbenes: Synthesis and photophysical properties

Hisamatsu et al.2017|Design and synthesis of tris-heteroleptic cyclometalated iridium | complexes consisting of three different nonsymmetric ligands based on ligand-selective electrophilic reactions via interligand HOMO hopping phenomena

Ricciardi et al.2016|Luminescent chiral ionic Ir | complexes: Synthesis and photophysical properties

US20130331577A1|2013-12-12|Preparation of a fac-isomer for a tris homoleptic metal complex

González et al.2018|Substituent influence in phenanthroline-derived ancillary ligands on the excited state nature of novel cationic Ir | complexes

ES2642114A1|2017-11-15|Complexes of iridium | of formula general [ir | 2 |] or [ir | 2 |] a |

TWI484020B|2015-05-11|Iridium complexes containing biazolate-based ligand

WO2009110199A1|2009-09-11|Near infrared strongly luminous rare earth complex

Tanaka et al.2020|Development of the sensitizer for generating higher-energy photons under diluted condition via the triplet-triplet annihilation-supported upconversion

Fiorini et al.2016|Fully Ir | tetrazolate soft salts: the road to white-emitting ion pairs

Vivancos et al.2021|Strongly Luminescent Pt | Complexes with a Mesoionic N-Heterocyclic Carbene Ligand: Tuning Their Photophysical Properties

Yu et al.2011|Synthesis, crystal structure and photoluminescence of iridium | coumarin complexes

Canisares et al.2020|Syntheses and characterization of Schiff base ligands and their Ir | complexes as coating for phosphor-converted LEDs

Lu et al.2018|Synthesis and characterization of Ag | and Au | complexes with macrocyclic hybrid amine N-heterocyclic carbene ligands

同族专利:

公开号 | 公开日

ES2642114B1|2018-05-22|

引用文献:

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

US20020134984A1|2001-02-01|2002-09-26|Fuji Photo Film Co., Ltd.|Transition metal complex and light-emitting device|

WO2004045001A2|2002-11-08|2004-05-27|Universal Display Corporation|Organic light emitting materials and devices|

US20080217606A1|2007-03-06|2008-09-11|Chien-Hong Cheng|Organic light emitting diode containing a Ir complex having a novel ligand as a phosphorescent emitter|

CN101481610A|2008-12-19|2009-07-15|太原理工大学|Organic phosphorescent material with iridium as inner core and preparation thereof|EP3865553A1|2020-02-14|2021-08-18|Samsung Electronics Co., Ltd.|Organometallic compound, organic light-emitting device including the same, and electronic apparatus including the organic light-emitting device|

法律状态:
2018-05-22| FG2A| Definitive protection|Ref document number: 2642114 Country of ref document: ES Kind code of ref document: B1 Effective date: 20180522 |

优先权:

申请号 | 申请日 | 专利标题

ES201630610A|ES2642114B1|2016-05-11|2016-05-11|IRIDIO COMPLEXESOF GENERAL FORMULA [Go2 ] or [Go2 ] A|ES201630610A| ES2642114B1|2016-05-11|2016-05-11|IRIDIO COMPLEXESOF GENERAL FORMULA [Go2 ] or [Go2 ] A|

[返回顶部]