三角形配位构型碘化亚铜配合物的合成、结构与性质
|
摘要
对两个新颖的碘化亚铜配合物CuI[2-(Dpp)bp]_2(配合物1,2-(Dpp)bp=二(二苯基膦)联苯)和Cu_2(μ-I)_2[TPP(o-OCH_3)]_2?CH_3CN (配合物2,TPP(o-OCH_3)=三(3-甲氧基苯基)膦)的合成、晶体结构和性质进行了研究。配合物1和配合物2分别表现为单核、双核碘化亚铜配合物的结构类型。在配合物1和2的晶体结构中,亚铜原子都表现为不同寻常的近乎平面的三角形配位构型,推测其原因可能是由于膦配体较大的空间位阻效应所致。两配合物都表现了良好的热稳定性,双核配合物2的热稳定性优于单核配合物1。配合物1和2的紫外-可见吸收主要来自于膦配体的π-π~*电子吸收跃迁,配合物1和2的能隙值分别为3.58、3.21 eV,说明配合物1和2均属于半导体。
The syntheses, structures and properties of two new cuprous iodide complexes, CuI[2-(Dpp)bp]_2(2-(Dpp)bp=2-(diphenylphosphino)-biphenyl) and Cu_2(μ-I)2[TPP(o-OCH_3)]_2·CH_3CN(TPP(o-OCH_3)= tri(3-methoxyphenyl)phosphine) were studied. The complex 1(CuI[2-(Dpp)bp]_2) andcomplex 2 showed structural styles of mononuclear and dinuclear cuprous iodide, respectively. In the crystal structures of complexes 1 and 2, cuprous atoms showed unusual near-planar triangle coordination geometry. This may be because of large steric-hinerance effect of phosphine ligand. The two complexes presented good thermal stability, and the thermal stability of dinuclear complex 2 was better than that of mononuclear complex 1. The UV-Vis absorption of the complexes 1 and 2 mainly came from the π-π~* electron transfer of the phosphine ligands. The band gaps of complexes 1 and 2 were 3.58 eV and 3.21 eV, respectively, indicating that the complexes belong to semiconductors.
The syntheses, structures and properties of two new cuprous iodide complexes, CuI[2-(Dpp)bp]_2(2-(Dpp)bp=2-(diphenylphosphino)-biphenyl) and Cu_2(μ-I)2[TPP(o-OCH_3)]_2·CH_3CN(TPP(o-OCH_3)= tri(3-methoxyphenyl)phosphine) were studied. The complex 1(CuI[2-(Dpp)bp]_2) andcomplex 2 showed structural styles of mononuclear and dinuclear cuprous iodide, respectively. In the crystal structures of complexes 1 and 2, cuprous atoms showed unusual near-planar triangle coordination geometry. This may be because of large steric-hinerance effect of phosphine ligand. The two complexes presented good thermal stability, and the thermal stability of dinuclear complex 2 was better than that of mononuclear complex 1. The UV-Vis absorption of the complexes 1 and 2 mainly came from the π-π~* electron transfer of the phosphine ligands. The band gaps of complexes 1 and 2 were 3.58 eV and 3.21 eV, respectively, indicating that the complexes belong to semiconductors.
引文
[1] 初国强,王子君,刘星元,等.有机电致发光现状和发展趋势[J].光机电信息,2001,18(8):14-19.
[2] Tang C W,Vanslyke S A,Chen C H.Electroluminescence of doped organic thin films[J].Journal of Applied Physics,1989,65(9):3610-3616.
[3] Adachi C,Tsutsui T,Saito S.Organic electroluminescent device having a hole conductor as an emitting layer[J].Applied Physics Letters,1989,55(15):1489-1491.
[4] Hsu C W,Lin C C,Chung M W,et al.Systematic investigation of the metal-structure photophysics relationship of emissive d10-complexes of group 11 elements:The prospect of application in organic light emitting devices[J].Journal of the American Chemical Society,2011,133(31):12085-12099.
[5] Chi Y,Chou P T.Transition-metal phosphors with cyclometalating ligands:Fundamentals and applications[J].Chemical Society Reviews 2010,39(2):638-655.
[6] Fujisawa K,Noguchi Y,Miyashita Y,et al.Mononuclear and binuclear copper(I) complexes ligated by bis(3,5-diisopropyl-1-pyrazolyl)methane:Insight into the fundamental coordination chemistry of three-coordinate copper(I) complexes with a neutral coligand[J].Inorganic Chemistry,2007,46(25):10607-10623.
[7] Ohara H,Ogawa T,Yoshida M,et al.Reversible luminescent colour changes of mononuclear copper(i) complexes based on ligand exchange reactions by N-heteroaromatic vapours[J].Dalton Transactions,2017,46(11):3755-3760.
[8] Anastasiadou D,Psomas G,Lalia-Kantouri M,et al.Copper(I) halide complexes of 2,2,5,5-tetramethyl-imidazolidine-4-thione:Synthesis,structures,luminescence,thermal stability and interaction with DNA[J].Materials Science and Engineering:C,2016,68:241-250.
[9] Maini L,Braga D,Mazzeo P P,et al.Polymorph and isomer conversion of complexes based on CuI and PPh3 easily observed via luminescence[J].Dalton Transactions,2012,41(2):531-539.
[10] Ananthnag G S,Edukondalu N,Mague J T,et al.Copper and palladium complexes of 2-(diphenylphosphino)-N,N-dimethylbenzylamine and its selenide derivative[J].Polyhedron,2013,62:203-207.
[11] Leitl M J,Küchle F R,Mayer H A,et al.Brightly Blue and Green Emitting Cu(I) dimers for Singlet Harvesting in OLEDs[J].The Journal of Physical Chemistry A,2013,117(46):11823-11836.
[12] Chen B L,Mok K F and Ng S C.Synthesis,crystal structures and dynamic NMR studies of novel trinuclear copper(I) halide complexes with 2,5-bis[(diphenylphosphino)-methyl]thiophene[J].Journal of the Chemical Society Dalton Transactions,1998,91(17):2861-2866.
[13] de Angelis F,Fantacci S,Sgamellotti A,et al.Electronic transitions involved in the absorption spectrum and dual luminescence of tetranuclear cubane [Cu4I4(pyridine)4] cluster:A density functional theory/time-dependent density functional theory investigation[J].Inorganic Chemistry,2006,45(26):10576-10584.
[14] Kitagawa H,Ozawa Y and Toriumi K.Flexibility of cubane-like Cu4I4 framework:Temperature dependence of molecular structure and luminescence thermochromism of [Cu4I4(PPh3)4] in two polymorphic crystalline states[J].Chemical Communications,2010,46(34):6302-6304.
[15] Perruchas S,Tard C,Le Goff X F,et al.Thermochromic luminescence of copper iodide clusters:The case of phosphine ligands[J].Inorganic Chemistry,2011,50(21):10682-10692.
[16] Chen A H,Meng S C,Zhang J F,et al.Syntheses,structural,theoretical studies and thermal behaviors of two luminous copper(I) halide complexes of dipyrido[3,2-f:2,3-h]-quinoxaline[J].Journal of Molecular Structure,2013,1050:15-20.
[17] Ohara H,Kobayashia A,Kato M.Simple and extremely efficient blue emitters based on mononuclear Cu(I)-halide complexes with delayed fluorescence[J].Dalton Transactions,2014,43(46):17317-17323.
[18] Sheldrick G M.SHELXS-97,Program for crystal structure solution[CP].Gottingen:University of G?tingen,1997.
[19] Cao G,Rabenberg L K,Nunn C M,et al.Formation of quantum-size semiconductor particles in a layered metal phosphonate host lattice[J].Chemistry of Materials,1991,3(1):149-156.
[20] Gholivand K,Farshadfer K,Roe S M,et al.Structural and photophysical characterization of mono- and binuclear Cu(I) complexes based on carbohydrazones:A combined experimental and computational study[J].CrystEngComm,2016,18(16):2873-2884.
[21] Zhang K,Zhang D.Synthesis and study on a series of phosphorescent Cu(I) complexes having sterically blocking ligands[J].Spectrochimica Acta Part A Molecular & Biomolecular Spectroscopy,2014,124(17):341-348.
[2] Tang C W,Vanslyke S A,Chen C H.Electroluminescence of doped organic thin films[J].Journal of Applied Physics,1989,65(9):3610-3616.
[3] Adachi C,Tsutsui T,Saito S.Organic electroluminescent device having a hole conductor as an emitting layer[J].Applied Physics Letters,1989,55(15):1489-1491.
[4] Hsu C W,Lin C C,Chung M W,et al.Systematic investigation of the metal-structure photophysics relationship of emissive d10-complexes of group 11 elements:The prospect of application in organic light emitting devices[J].Journal of the American Chemical Society,2011,133(31):12085-12099.
[5] Chi Y,Chou P T.Transition-metal phosphors with cyclometalating ligands:Fundamentals and applications[J].Chemical Society Reviews 2010,39(2):638-655.
[6] Fujisawa K,Noguchi Y,Miyashita Y,et al.Mononuclear and binuclear copper(I) complexes ligated by bis(3,5-diisopropyl-1-pyrazolyl)methane:Insight into the fundamental coordination chemistry of three-coordinate copper(I) complexes with a neutral coligand[J].Inorganic Chemistry,2007,46(25):10607-10623.
[7] Ohara H,Ogawa T,Yoshida M,et al.Reversible luminescent colour changes of mononuclear copper(i) complexes based on ligand exchange reactions by N-heteroaromatic vapours[J].Dalton Transactions,2017,46(11):3755-3760.
[8] Anastasiadou D,Psomas G,Lalia-Kantouri M,et al.Copper(I) halide complexes of 2,2,5,5-tetramethyl-imidazolidine-4-thione:Synthesis,structures,luminescence,thermal stability and interaction with DNA[J].Materials Science and Engineering:C,2016,68:241-250.
[9] Maini L,Braga D,Mazzeo P P,et al.Polymorph and isomer conversion of complexes based on CuI and PPh3 easily observed via luminescence[J].Dalton Transactions,2012,41(2):531-539.
[10] Ananthnag G S,Edukondalu N,Mague J T,et al.Copper and palladium complexes of 2-(diphenylphosphino)-N,N-dimethylbenzylamine and its selenide derivative[J].Polyhedron,2013,62:203-207.
[11] Leitl M J,Küchle F R,Mayer H A,et al.Brightly Blue and Green Emitting Cu(I) dimers for Singlet Harvesting in OLEDs[J].The Journal of Physical Chemistry A,2013,117(46):11823-11836.
[12] Chen B L,Mok K F and Ng S C.Synthesis,crystal structures and dynamic NMR studies of novel trinuclear copper(I) halide complexes with 2,5-bis[(diphenylphosphino)-methyl]thiophene[J].Journal of the Chemical Society Dalton Transactions,1998,91(17):2861-2866.
[13] de Angelis F,Fantacci S,Sgamellotti A,et al.Electronic transitions involved in the absorption spectrum and dual luminescence of tetranuclear cubane [Cu4I4(pyridine)4] cluster:A density functional theory/time-dependent density functional theory investigation[J].Inorganic Chemistry,2006,45(26):10576-10584.
[14] Kitagawa H,Ozawa Y and Toriumi K.Flexibility of cubane-like Cu4I4 framework:Temperature dependence of molecular structure and luminescence thermochromism of [Cu4I4(PPh3)4] in two polymorphic crystalline states[J].Chemical Communications,2010,46(34):6302-6304.
[15] Perruchas S,Tard C,Le Goff X F,et al.Thermochromic luminescence of copper iodide clusters:The case of phosphine ligands[J].Inorganic Chemistry,2011,50(21):10682-10692.
[16] Chen A H,Meng S C,Zhang J F,et al.Syntheses,structural,theoretical studies and thermal behaviors of two luminous copper(I) halide complexes of dipyrido[3,2-f:2,3-h]-quinoxaline[J].Journal of Molecular Structure,2013,1050:15-20.
[17] Ohara H,Kobayashia A,Kato M.Simple and extremely efficient blue emitters based on mononuclear Cu(I)-halide complexes with delayed fluorescence[J].Dalton Transactions,2014,43(46):17317-17323.
[18] Sheldrick G M.SHELXS-97,Program for crystal structure solution[CP].Gottingen:University of G?tingen,1997.
[19] Cao G,Rabenberg L K,Nunn C M,et al.Formation of quantum-size semiconductor particles in a layered metal phosphonate host lattice[J].Chemistry of Materials,1991,3(1):149-156.
[20] Gholivand K,Farshadfer K,Roe S M,et al.Structural and photophysical characterization of mono- and binuclear Cu(I) complexes based on carbohydrazones:A combined experimental and computational study[J].CrystEngComm,2016,18(16):2873-2884.
[21] Zhang K,Zhang D.Synthesis and study on a series of phosphorescent Cu(I) complexes having sterically blocking ligands[J].Spectrochimica Acta Part A Molecular & Biomolecular Spectroscopy,2014,124(17):341-348.