Tuning Electronic Structure, Redox, and Photophysical Properties in Asymmetric NIR-Absorbing Organometallic BODIPYs

被引:64
作者
Zatsikha, Yuriy V. [1 ,2 ]
Maligaspe, Eranda [1 ]
Purchel, Anatolii A. [1 ]
Didukh, Natalia O. [2 ]
Wang, Yefeng [3 ]
Kovtun, Yuriy P. [2 ]
Blank, David A. [3 ]
Nemykin, Victor N. [1 ]
机构
[1] Univ Minnesota Duluth, Dept Chem & Biochem, Duluth, MN 55812 USA
[2] Natl Acad Sci Ukraine, Inst Organ Chem, UA-02660 Kiev, Ukraine
[3] Univ Minnesota, Dept Chem, Minneapolis, MN 55455 USA
基金
美国国家科学基金会;
关键词
PHOTOINDUCED CHARGE-TRANSFER; DONOR-ACCEPTOR DYADS; MIXED-VALENCE STATES; METAL-FREE; FERROCENYL PORPHYRINS; CORRELATION-ENERGY; FULLERENE; BORON; ELECTROCHEMISTRY; PHTHALOCYANINE;
D O I
10.1021/acs.inorgchem.5b00992
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Stepwise modification of the methyl groups at the a positions of BODIPY 1 was used for preparation of a series of mono- (2, 4, and 6) and diferrocene (3) substituted donor acceptor dyads in which the organometallic substituents are fully conjugated with the BODIPY 7t system. All donor-acceptor complexes have strong absorption in the NIR region and quenched steady-state fluorescence, which can be partially restored upon oxidation of organometallic group(s). X-ray crystallography of complexes 2-4 and 6 confirms the nearly coplanar arrangement of the ferrocene groups and the BODIPY re system. Redox properties of the target systems BODIPY re system. Redox properties of the target systems were studied using cyclic voltammetry (CV) and differential pulse voltammetry (DPV). It was found that the first oxidation process in all dyads is ferrocene centered, while the separation between the first and the second ferrocene-centered oxidation potentials in diferrocenyl-containing dyad 3 is 150 mV. The density functional theory-polarized continuum model (DFTPCM) and time-dependent (TD) DFT-PCM methods were used to investigate the electronic structure as well as explain the UV vis and redox properties of organometallic compounds 2-4 and 6. TDDFT calculations allow for assignment of the chargetransfer and pi ->pi transitions in the target compounds. The excited state dynamics of the parent BODIPY 1 and dyads 2-4 and 6 were investigated using time-resolved transient spectroscopy. In all organometallic dyads 2-4 and 6 the initially excited state is rapidly quenched by electron transfer from the ferrocene ligand. The lifetime of the charge-separated state was found to be between 136 and 260 ps and demonstrates a systematic dependence on the electronic structure and geometry of BODIPYs 2-4 and 6.
引用
收藏
页码:7915 / 7928
页数:14
相关论文
共 133 条
[1]   Theoretical investigation of the (hyper) polarizabilities of pyrrole homologues C4H4XH (X = N, P, As, Sb, Bi).: A coupled-cluster and density functional theory study [J].
Alparone, Andrea ;
Reis, Heribert ;
Papadopoulos, Manthos G. .
JOURNAL OF PHYSICAL CHEMISTRY A, 2006, 110 (17) :5909-5918
[2]   SIR92 - a program for automatic solution of crystal structures by direct methods [J].
ALTOMARE, A ;
CASCARANO, G ;
GIACOVAZZO, G ;
GUAGLIARDI, A ;
BURLA, MC ;
POLIDORI, G ;
CAMALLI, M .
JOURNAL OF APPLIED CRYSTALLOGRAPHY, 1994, 27 :435-435
[3]   Syntheses, Electrochemistry, and Photodynamics of Ferrocene-Azadipyrromethane Donor-Acceptor Dyads and Triads [J].
Amin, Anu N. ;
El-Khouly, Mohamed E. ;
Subbaiyan, Navaneetha K. ;
Zandler, Melvin E. ;
Supur, Mustafa ;
Fukuzumi, Shunichi ;
D'Souza, Francis .
JOURNAL OF PHYSICAL CHEMISTRY A, 2011, 115 (35) :9810-9819
[4]   Synthesis and Characterization of Peripherally Ferrocene-modified Zinc Phthalocyanine for Dye-sensitized Solar Cell [J].
An, Minshi ;
Kim, Soonwha ;
Hong, Jong-Dal .
BULLETIN OF THE KOREAN CHEMICAL SOCIETY, 2010, 31 (11) :3272-3278
[5]  
[Anonymous], 2008, ANGEW CHEM
[6]  
[Anonymous], J ORGANOMET CHEM
[7]  
[Anonymous], YOUJI HUAXUE
[8]  
[Anonymous], CHEM PHYS LETT
[9]  
[Anonymous], ORGANIC ELECT PHOTON
[10]  
Aratani N., 2010, HDB PORPHYRIN SCI, V1, P1