Electronic structure and bridge geometric distortion in push-pull imine-bridged triads. A theoretical study

被引:1
作者
Espinosa Ferao, Arturo [1 ]
Garcia Alcaraz, Antonio [1 ]
Garcia Lopez, Rafaela [1 ]
机构
[1] Univ Murcia, Fac Quim, Dept Quim Organ, Campus Espinardo, Murcia 30100, Spain
关键词
NONLINEAR-OPTICAL-PROPERTIES; ZETA VALENCE QUALITY; ORGANIC-SOLID-STATE; AQUEOUS ENVIRONMENT; CATION RECOGNITION; HARTREE-FOCK; BASIS-SETS; REDOX; FLUORESCENT; DERIVATIVES;
D O I
10.1039/d1nj00152c
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The Intramolecular Electron Transfer (IET) in a wide set of imine-bridged triads as well as some model ethylene-bridged compounds and directly linked donor-acceptor diads was explored, using ferrocene and quinone groups as prototypical donor and acceptor subunits, respectively. For this purpose, the electric charge transferred from and to each subunit was analysed and some global electronic descriptors (dipole moment and chemical hardness) were computed. Ferrocene geometric distortion parameters (namely the Fe-Cp distance, total transannular deflection angle and the fulvenization HOMFc descriptor) also provided a reliable picture of IET for only ferrocenyl-substituted diads or triads. A new "Harmonic Oscillator Model of Conjugated Ethylene character" (HOMCEc) parameter was proposed in order to estimate the extension to which the bridge is engaged in IET taking place in ethylene-bridged compounds and derivatives (e.g. imines).
引用
收藏
页码:4472 / 4480
页数:9
相关论文
共 91 条
[1]   Tuning first molecular hyperpolarizabilities through the use of proaromatic spacers [J].
Andreu, R ;
Blesa, MJ ;
Carrasquer, L ;
Garín, J ;
Orduna, J ;
Villacampa, B ;
Alcalá, R ;
Casado, J ;
Delgado, MCR ;
Navarrete, JTL ;
Allain, M .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (24) :8835-8845
[2]   Decreased Optical Nonlinearities upon CF3 Substitution on Tricyanofuran Acceptors [J].
Andreu, Raquel ;
Angel Cerdan, Miguel ;
Franco, Santiago ;
Garin, Javier ;
Belen Marco, Ana ;
Orduna, Jesus ;
Palomas, David ;
Villacampa, Belen ;
Alicante, Raquel ;
Allain, Magali .
ORGANIC LETTERS, 2008, 10 (21) :4963-4966
[3]   Luminescent and redox-active polynuclear transition metal complexes [J].
Balzani, V ;
Juris, A ;
Venturi, M ;
Campagna, S ;
Serroni, S .
CHEMICAL REVIEWS, 1996, 96 (02) :759-833
[4]  
Balzani V., 2001, ELECT TRANSFER CHEM, V1-5
[5]   ELECTROCHEMICAL AND INFRARED-SPECTROSCOPIC CHARACTERIZATION OF REDOX REACTIONS OF P-QUINONES [J].
BAUSCHER, M ;
MANTELE, W .
JOURNAL OF PHYSICAL CHEMISTRY, 1992, 96 (26) :11101-11108
[6]   DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE [J].
BECKE, AD .
JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07) :5648-5652
[7]   A NOVEL PORPHYRIN-FERROCENE-QUINONE LINKED MOLECULE [J].
BEER, PD ;
KUREK, SS .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1989, 366 (1-2) :C6-C8
[8]   PUSH-PULL POLYENES AND CAROTENOIDS - SYNTHESIS AND NON-LINEAR OPTICAL-PROPERTIES [J].
BLANCHARDDESCE, M ;
LEDOUX, I ;
LEHN, JM ;
MALTHETE, J ;
ZYSS, J .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1988, (11) :737-739
[9]   B97-3c: A revised low-cost variant of the B97-D density functional method [J].
Brandenburg, Jan Gerit ;
Bannwarth, Christoph ;
Hansen, Andreas ;
Grimme, Stefan .
JOURNAL OF CHEMICAL PHYSICS, 2018, 148 (06)
[10]   SOLVENT REORGANIZATION IN OPTICAL AND THERMAL ELECTRON-TRANSFER PROCESSES - SOLVATOCHROMISM AND INTRAMOLECULAR ELECTRON-TRANSFER BARRIERS IN SPHEROIDAL MOLECULES [J].
BRUNSCHWIG, BS ;
EHRENSON, S ;
SUTIN, N .
JOURNAL OF PHYSICAL CHEMISTRY, 1987, 91 (18) :4714-4723