Solution and solid-state properties of luminescent M-M bond-containing coordination/organometallic polymers using the RNC-M2(dppm)2-CNR building blocks (M = Pd, Pt; R = aryl, alkyl)

被引:29
作者
Bérubé, JF
Gagnon, K
Fortin, D
Decken, A
Harvey, PD [1 ]
机构
[1] Univ Sherbrooke, Dept Chim, Sherbrooke, PQ J1K 2R1, Canada
[2] Univ New Brunswick, Dept Chem, Fredericton, NB E3B 6E2, Canada
关键词
D O I
10.1021/ic0509480
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Two families of organometallic polymers built upon the bimetallic M-2(dPPM)(2)L-2(2+) fragments (M = Pd, Pt; dppm = bis(diphenylphosphino)methane, L = 1,4-diisocyano-2,3,5,6-tetramethylbenzene (diiso), 1,8-diisocyano-p-menthane (dmb), 1-isocyano-2,6-dimethylbenzene, 1-isocyano-4-isopropylbenzene, and tert-butylisocyanide) were synthesized and fully characterized (H-1 and P-31 NMR, X-ray crystallography (model compounds), IR, Raman, chem. anal., TGA, DSC, powder XRD, P-31 NMR T, and NOE, light scattering, and conductivity measurements). Evidence for polymers in the solid state is provided from the swelling of the polymers upon dissolution and the formation of stand-alone films. However, these species become small oligomers when dissolved. The materials are luminescent in the solid state at 298 and 77 K and in PrCN solution at 77 K. These emissions result from triplet (3)(d sigma d sigma*) states despite the presence of low-lying pi-pi* MO levels according to DFT calculations for the aryl isocyanide model compounds. The emission band maxima are located between 640 and 750 nm and exhibit lifetimes of 3-6 ns for the Pd species and 3-4 mu s for the Pt analogues in PrCN solution at 77 K. No evidence of intramolecular excitonic photoprocesses was found in any of the polymers.
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页码:2812 / 2823
页数:12
相关论文
共 83 条
[21]   DIFRAC, SINGLE-CRYSTAL DIFFRACTOMETER OUTPUT-CONVERSION SOFTWARE [J].
FLACK, HD ;
BLANC, E ;
SCHWARZENBACH, D .
JOURNAL OF APPLIED CRYSTALLOGRAPHY, 1992, 25 (pt 3) :455-459
[22]   Organometallic oligomers based on 1,8-diisocyano-p-menthane (dmlb):: Syntheses and characterization of the {[M(diphos)(dmb)]BF4}n and {[Pd2(diphos)2(dmb)](ClO4)2}n Materials (M = Cu, Ag; diphos = dppe, dppp) [J].
Fournier, E ;
Sicard, S ;
Decken, A ;
Harvey, PD .
INORGANIC CHEMISTRY, 2004, 43 (04) :1491-1501
[23]   Organometallic polymers: Synthesis and electro-optical properties [J].
Fratoddi, I ;
Altamura, P ;
Lo Sterzo, C ;
Furlani, A ;
Galassi, E ;
D'Amico, A ;
Russo, MV .
POLYMERS FOR ADVANCED TECHNOLOGIES, 2002, 13 (3-4) :269-274
[24]  
Frisch M.J., 2016, Gaussian 16 Revision C. 01. 2016, V01
[25]   NRCVAX - AN INTERACTIVE PROGRAM SYSTEM FOR STRUCTURE-ANALYSIS [J].
GABE, EJ ;
LEPAGE, Y ;
CHARLAND, JP ;
LEE, FL ;
WHITE, PS .
JOURNAL OF APPLIED CRYSTALLOGRAPHY, 1989, 22 :384-387
[26]   MOLECULAR-STRUCTURE OF HEXAKIS(METHYL ISOCYANIDE)DIPALLADIUM(I) BIS(HEXAFLUOROPHOSPHATE) HEMIACETONE, [PD2(CNME)6](PF6)2-1/2ME2CO - PALLADIUM(I) DIMER [J].
GOLDBERG, SZ ;
EISENBERG, R .
INORGANIC CHEMISTRY, 1976, 15 (03) :535-541
[27]   RESONANCE-ENHANCED INTRALIGAND AND METAL-METAL RAMAN MODES IN WEAKLY METAL METAL-INTERACTING PLATINUM(II) COMPLEXES AND LONG-RANGE RELATIONSHIP BETWEEN METAL-METAL SEPARATIONS AND FORCE-CONSTANTS [J].
HARVEY, PD ;
TRUONG, KD ;
AYE, KT ;
DROUIN, M ;
BANDRAUK, AD .
INORGANIC CHEMISTRY, 1994, 33 (11) :2347-2354
[28]   PROPERTIES OF PD(I)-PD(I) BONDS - THEORETICAL AND SPECTROSCOPIC STUDY OF PD2(DMB)2X2 COMPLEXES (DMB = 1,8-DIISOCYANO-P-MENTHANE, X = CL,BR) [J].
HARVEY, PD ;
MURTAZA, Z .
INORGANIC CHEMISTRY, 1993, 32 (22) :4721-4729
[29]  
HARVEY PD, 2005, IN PRESS ACS BOOKS
[30]  
Harvey PD, 2005, MACROMOL CONTAIN MET, V5, P83