Structural and Luminescence Studies on π•••π and Pt•••Pt Interactions in Mixed Chloro-lsocyanide Cyclometalated Platinum(II) Complexes

被引:119
作者
Diez, Alvaro [1 ]
Fornies, Juan [2 ]
Larraz, Carmen [2 ]
Lalinde, Elena [1 ]
Lopez, Jose A. [2 ]
Martin, Antonio [2 ]
Teresa Moreno, M. [1 ]
Sicilia, Violeta [3 ]
机构
[1] Univ La Rioja, Dept Quim, Grp Sintesis Quim La Rioja, UA CSIC, Logrono 26006, Spain
[2] Univ Zaragoza, Dept Quim Inorgan, Inst Ciencia Mat Aragon, Fac Ciencias,CSIC, E-50009 Zaragoza, Spain
[3] Univ Zaragoza, Dept Quim Inorgan, Inst Ciencia Mat Aragon, Escuela Univ Ingn Tecn Ind,CSIC, Zaragoza 50018, Spain
关键词
SOLVENT-INDUCED AGGREGATION; SPECTROSCOPIC PROPERTIES; METAL-METAL; ELECTROLUMINESCENT PROPERTIES; PHOTOPHYSICAL PROPERTIES; ELECTRONIC SPECTROSCOPY; INFRARED-SPECTROSCOPY; TERPYRIDYL COMPLEXES; CRYSTAL-STRUCTURES; EXCIMER FORMATION;
D O I
10.1021/ic902094c
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
[Pt(bzq)CI(CNR)] [bzq = benzoquinolinate; R = tert-butyl (Bu-1 1), 2-6-dimethylphenyl (Xyl 2), 2-naphthyl (2-Np 3)] complexes have been synthesized and structurally and photophysically characterized. 1 was found to co-crystallize in two distinct pseudopolymorphs: a red form, which exhibits an infinite 1D-chain ([1](infinity)) and a yellow form, which contains discrete dimers ([1](2)), both stabilized by interplanar pi center dot center dot center dot pi (bzq) and short Pt center dot center dot center dot Pt bonding interactions. Complex 3, generated through the unexpected garnet-red double salt isomer [Pt(bzq)(CN-2-Np)(2)][Pt(bzq)Cl-2] 4, crystallizes as yellow Pt center dot center dot center dot Pt dimers ([3](2)), while 2 only forms pi center dot center dot center dot pi (bzq) contacting dimers, Their electronic absorption and luminescence behaviors have been investigated. According to Time-Dependent Density Functional Theory (TD-DFT) calculations, the lowest-lying absorption (CH2Cl2) has been attributed to combined (ILCT)-I-1 and (MLCT)-M-1/(ML)-M-1'CT (L = bzq, L' = CNR) transitions, the latter increasing from 1 to 3. In solid state, while the yellow form [1](2) exhibits a green (MLCT)-M-3 unstructured emission only at 77 K, the 1-D form [1](infinity) displays a characteristic low-energy red emission (672 nm, 298 K; 744 nm, 77 K) attributed to a mixed 3MMCT [d(sigma*) p(sigma)]/(MMLCT)-M-3 [d sigma*(M-2)->sigma(pi*)(bzq)] excited state. However, upon exposure to standard atmospheric conditions, Ii],.. shows an irreversible change to an orangeochre solid, whose emissive properties are similar to those of the crude 1. Complexes 2 and 3 (77 K) exhibit a structured emission from discrete fragments ((LC)-L-3/(MLCT)-M-3), whereas the luminescence of the garnet-red salt 4 is dominated by a low energy emission (680 nm, 298 K; 730 nm, 77 K) arising from a (MMLCT)-M-3 excited state. Solvent (CH2Cl2, toluene, 2-MeTHF and CH3CN) and concentration-dependent emission studies at 298 K and at 77 K are also reported for 1-3. In CH2Cl2 solution, the low phosphorescent emission band is ascribed to bzq intraligand charge transfer (ILCT)-I-3 mixed with metal-to-ligand (L = bzq, L' = CNR) charge transfer (MLCT)-M-3/(ML)-M-3'CT character with the Pt to CNR contribution increasing from 1 to 3, according to computational studies.
引用
收藏
页码:3239 / 3251
页数:13
相关论文
共 98 条
[1]   Luminescence color change of a platinum(II) complex solid upon mechanical grinding [J].
Abe, Taichi ;
Itakura, Toru ;
Ikeda, Noriaki ;
Shinozaki, Kazuteru .
DALTON TRANSACTIONS, 2009, (04) :711-715
[2]   Platinum Stacking Interactions in Homoleptic Platinum Polymers [J].
Anderson, Bernard M. ;
Hurst, Stephanie K. .
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2009, (21) :3041-3054
[3]   Chain conformation and metal center dot center dot center dot metal contacts in dimers and stacks of d(8)-ML4 complexes: Electronic effects [J].
Aullon, G ;
Alvarez, S .
CHEMISTRY-A EUROPEAN JOURNAL, 1997, 3 (04) :655-664
[4]   ELECTRONIC SPECTROSCOPY OF CHLORO(TERPYRIDINE)PLATINUM(II) [J].
BAILEY, JA ;
HILL, MG ;
MARSH, RE ;
MISKOWSKI, VM ;
SCHAEFER, WP ;
GRAY, HB .
INORGANIC CHEMISTRY, 1995, 34 (18) :4591-4599
[5]   Dynamic Crystals: Visually Detected Mechanochemical Changes in the Luminescence of Gold and Other Transition-Metal Complexes [J].
Balch, Alan L. .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2009, 48 (15) :2641-2644
[6]   DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE [J].
BECKE, AD .
JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07) :5648-5652
[7]   DENSITY-FUNCTIONAL EXCHANGE-ENERGY APPROXIMATION WITH CORRECT ASYMPTOTIC-BEHAVIOR [J].
BECKE, AD .
PHYSICAL REVIEW A, 1988, 38 (06) :3098-3100
[8]   Energy Transfers in Monomers, Dimers, and Trimers of Zinc(II) and Palladium(II) Porphyrins Bridged by Rigid Pt-Containing Conjugated Organometallic Spacers [J].
Bellows, Diana ;
Aly, Shawkat M. ;
Gros, Claude P. ;
El Ojaimi, Maya ;
Barbe, Jean-Michel ;
Guilard, Roger ;
Harvey, Pierre D. .
INORGANIC CHEMISTRY, 2009, 48 (16) :7613-7629
[9]   Synthesis, characterization and photophysics of a new series of anionic C,N,C cyclometalated platinum complexes [J].
Berenguer, Jesus R. ;
Lalinde, Elena ;
Torroba, Javier .
INORGANIC CHEMISTRY, 2007, 46 (23) :9919-9930
[10]  
Beursken P. T., 1992, DIRDIF92 PROGRAM SYS