Electrochemical Variational Study of Donor/ Acceptor Orbital Mixing and Electronic Coupling in CyanideBridged Mixed-Valence Complexes

نویسنده

  • Yuhua Dong
چکیده

Cyanide-bridged mixed-valence complexes featuring metal(111) pentaammine acceptor sites and metal(I1) hexacyano donor sites have been investigated extensively by Vogler et aI.,l Haim and Burewicz,2 Shepherd et al.,3 and otherse4 These complexes are interesting examples of strongly covalently linked redox systems which, nevertheless, exist in valence-localized form. As mixed-valence species, they display fairly intense intervalence (or metal-to-metal) charge-transfer transitions ( E = 3000 M-I cm-I), which tend to be shifted toward the visible region from the near-infrared on account of substantial redox Our own interests center on bridge-mediated charge-transfer kinetics. We have recently succeeded5 in obtaining (by femtosecond transient absorbance spectroscopy) a direct measure of the thermal kinetics ET) of the highly exothermic back-electrontransfer reaction which follows intervalence excitation in one of these complexes, (H3N) jRu-NC-Fe( CN),-:

برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید

ثبت نام

اگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید

منابع مشابه

Electrochemical and Spectral Probes of Metal/Ligand Orbital Mixing in

An electrochemical variational method (de la Rosa, et al. Inorg. Chem. 1985,24,4229) has been used to examine experimentally the extent of metal/ligand orbital mixing and electronic coupling in complexes of the type Ru"(NHJ4L2+ (L = 2,2'-bipyridine or 1 ,IO-phenanthroline). From the experiments, strong localization of d r electrons at the ruthenium metal center is indicated, Nevertheless, some ...

متن کامل

Reduced electronic spaces for modeling donor/acceptor interactions.

Diabatic states for donor (D) and acceptor (A) interactions in electron transfer (ET) processes are formulated and evaluated, along with coupling elements (H(DA)) and effective D/A separation distances (r(DA)), for reduced electronic spaces of variable size, using the generalized Mulliken Hush model (GMH), applicable to an arbitrary state space and nuclear configuration, and encompassing Robin-...

متن کامل

TTF-Based Mixed-Valence Acceptor-Donor-Acceptor Triads: A Joint Theoretical and Experimental Approach

This work presents a joint theoretical and experimental characterization of the structural and electronic properties of two tetrathiafulvalene (TTF)-based acceptor-donor-acceptor triads (BQTTF-BQ and BTCNQ-TTF-BTCNQ, where BQ is naphthoquinone and BTCNQ is benzotetracyano-p-quinodimethane) in their neutral and reduced states. The study is performed making use of electrochemical, electron parama...

متن کامل

Electron Transfer through Thin Organic Films and Highly Curved Donor- Bridge-Acceptor Molecules

Electron-transfer rate constants were measured for a variety of molecular systems. The rate constant was found to depend upon the nature of the medium between the electron donor and acceptor moieties. Using a superexchange model to calculate the electronic coupling between donor and acceptor, the effect of orbital energetics was studied. For photoinduced electron transfer, aromatic moieties wit...

متن کامل

Mutual interplay between interactions of pi electrons with simultaneous σ-hole interactions: A computational Study

In this study, the role of interaction of pi electrons on the strength of simultaneous σ-hole interactions (pnicogen, chalcogen and halogen bonds) is investigated using the quantum chemical calculations. X-ben||TAZ∙∙∙Y1,Y2,Y3 complexes (X = CN, F, Cl, Br, CH3 , OH and NH2, TAZ= s-triazine and Y1,Y2 and Y3 denotes PH2F, HSF, and ClF molecules) is introduced as a model. The results show that inte...

متن کامل

ذخیره در منابع من


  با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید

برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید

ثبت نام

اگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید

عنوان ژورنال:

دوره   شماره 

صفحات  -

تاریخ انتشار 2001