A photoinduced mixed valence photoswitch

被引：9

作者：

Cotic, Agustina ^{[1
,2
]}

Cerfontaine, Simon ^{[3
]}

Slep, Leonardo D. ^{[1
,2
]}

Elias, Benjamin ^{[3
]}

Troian-Gautier, Ludovic ^{[3
]}

Cadranel, Alejandro ^{[1
,2
,4
,5
]}

机构：

[1] Univ Buenos Aires, Fac Ciencias Exactas & Nat, Dept Quim Inorgan Analit & Quim Fis, Pabellon 2,Ciudad Univ,C1428EHA, Buenos Aires, DF, Argentina

[2] Univ Buenos Aires, Inst Quim Fis Mat Medio Ambiente & Energia INQUIM, CONICET, Pabellon 2,Ciudad Univ,C1428EHA, Buenos Aires, DF, Argentina

[3] Univ Catholique Louvain UCLouvain, Inst Matiere Condensee & Nanosci IMCN, Mol Chem Mat & Catalysis MOST, Pl Louis Pasteur 1,Bte L4-01-02, B-1348 Louvain La Neuve, Belgium

[4] Friedrich Alexander Univ Erlangen Nurnberg FAU, Phys Chem 1, Egerlandstr 3, D-91058 Erlangen, Germany

[5] Friedrich Alexander Univ Erlangen Nurnberg FAU, Interdisciplinary Ctr Mol Mat, Egerlandstr 3, D-91058 Erlangen, Germany

来源：

PHYSICAL CHEMISTRY CHEMICAL PHYSICS | 2022年 / 24卷 / 24期

关键词：

TRANSIENT ABSORPTION-SPECTROSCOPY; STATE INTERVALENCE TRANSFER; ELECTRON-TRANSFER; POLYPYRIDINE COMPLEXES; CORRESPONDING ORBITALS; RUTHENIUM(II); TRINUCLEAR; SYSTEMS; 2,2'-BIPYRIDINE; 4,4'-BIPYRIDINE;

D O I：

10.1039/d2cp01791a

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The ground state and photoinduced mixed valence states (GSMV and PIMV, respectively) of a dinuclear (Dp(4+)) ruthenium(ii) complex bearing 2,2 '-bipyridine ancillary ligands and a 2,2 ':4 ',4 '':2 '',2 '''-quaterpyridine (Lp) bridging ligand were investigated using femtosecond and nanosecond transient absorption spectroscopy, electrochemistry and density functional theory. It was shown that the electronic coupling between the transiently light-generated Ru(ii) and Ru(iii) centers is H-DA similar to 450 cm(-1) in the PIMV state, whereas the electrochemically generated GSMV state showed H-DA similar to 0 cm(-1), despite virtually identical Ru-Ru distances. This stemmed from the changes in dihedral angles between the two bpy moieties of Lp, estimated at 30 degrees and 4 degrees for the GSMV and PIMV states, respectively, consistent with a through-bond rather than a through-space mechanism. Electronic coupling can be turned on by using visible light excitation, making Dp(4+) a competitive candidate for photoswitching applications. A novel strategy to design photoinduced charge transfer molecular switches is proposed.

引用

页码：15121 / 15128

页数：8

共 68 条

[11] Generalization of the Mulliken-Hush treatment for the calculation of electron transfer matrix elements [J].