Detection of the Singlet and Triplet MM δδ* States in Quadruply Bonded Dimetal Tetracarboxylates (M = Mo, W) by Time-Resolved Infrared Spectroscopy

被引：23

作者：

Alberding, Brian G. ^{[1
]}

Chisholm, Malcolm H. ^{[1
]}

Gustafson, Terry L. ^{[1
]}

机构：

[1] Ohio State Univ, Dept Chem, Columbus, OH 43210 USA

来源：

INORGANIC CHEMISTRY | 2012年 / 51卷 / 01期

基金：

美国国家科学基金会;

关键词：

RADIATIONLESS PROCESSES; COMPLEXES; SPECTRA; RAMAN; MO2(O2CCH3)4; BEHAVIOR;

D O I：

10.1021/ic201957a

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The compounds M-2((O2CBu)-Bu-t)(4) and M-2(O2CC6H5)(4), where M = Mo or W, have been examined by femtosecond time-resolved IR (fs-TRIR) spectroscopy in tetrahydrofuran with excitation into the singlet metal-to-ligand charge-transfer ((MLCT)-M-1) band. In the region from 1500 to 1600 cm(-1), a long-lived excited state (>2 ns) has been detected for the compounds M-2((O2CBu)-Bu-t)(4) and Mo-2(O2CC6H5)(4) with an IR absorption at similar to 1540 cm(-1) assignable to the asymmetric CO2 stretch, nu(as)(CO2), of the triplet metal-metal delta-delta star ((MM)-M-3 delta delta*) state. The fs-TRIR spectra of W-2(O2CC6H5)(4) are notably different and are assigned to decay of the MLCT states. In (MM)-M-3 delta delta*, the removal of an electron from the delta orbital reduces MM delta to CO2 pi* back-bonding and causes, a shift of nu(as)(CO2) to higher energy by similar to 30-60 cm(-1) depending on the metal. TRIR spectroscopy also provides evidence for M-2((O2CBu)-Bu-t)(4), where M = Mo or W, having MM delta delta* S-1 states with nu(as)(CO2) distinct from those of the (MM)-M-3 delta delta* states.

引用

页码：491 / 498

页数：8

共 32 条

[1] Electron delocalization in the S1 and T1 metal-to-ligand charge transfer states of trans-substituted metal quadruply bonded complexes [J].

Alberding, Brian G. ;

Chisholm, Malcolm H. ;

Gallucci, Judith C. ;

Ghosh, Yagnaseni ;

Gustafson, Terry L. .

PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 2011, 108 (20) :8152-8156

[2] Photophysical Studies of trans-Bis(phenylethynyldiisopropylamidinato)bis(acetato)dimetal Complexes Involving MM Quadruple Bonds Where M = Mo or W [J].

Alberding, Brian G. ;

Chisholm, Malcolm H. ;

Gustafson, Terry L. ;

Liu, Yao ;

Reed, Carly R. ;

Turro, Claudia .

JOURNAL OF PHYSICAL CHEMISTRY A, 2010, 114 (48) :12675-12681

[3] Molecular, electronic structure and spectroscopic properties of MM quadruply bonded units supported by trans-6-carboethoxy-2-carboxylatoazulene ligands [J].

Alberding, Brian G. ;

Barybin, Mikhail V. ;

Chisholm, Malcolm H. ;

Gustafson, Terry L. ;

Reed, Carly R. ;

Robinson, Randall E. ;

Patmore, Nathan J. ;

Singh, Namrata ;

Turro, Claudia .

DALTON TRANSACTIONS, 2010, 39 (08) :1979-1984

[4] 2-Thienylcarboxylato and 2-Thienylthiocarboxylato Ligands Bonded to MM Quadruple Bonds (M = Mo or W): A Comparison of Ground State, Spectroscopic and Photoexcited State Properties [J].

Alberding, Brian G. ;

Chisholm, Malcolm H. ;

Chou, Yi-Hsuan ;

Ghosh, Yagnaseni ;

Gustafson, Terry L. ;

Liu, Yao ;

Turro, Claudia .

INORGANIC CHEMISTRY, 2009, 48 (23) :11187-11195

[5] Quadruply Bonded Dimetal Units Supported by 2,4,6-Triisopropylbenzoates MM(TiPB)4 (MM = Mo2, MoW, and W2): Preparation and Photophysical Properties [J].

Alberding, Brian G. ;

Chisholm, Malcolm H. ;

Chou, Yi-Hsuan ;

Gallucci, Judith C. ;

Ghosh, Yagnaseni ;

Gustafson, Terry L. ;

Patmore, Nathan J. ;

Reed, Carly R. ;

Turro, Claudia .

INORGANIC CHEMISTRY, 2009, 48 (10) :4394-4399

[6] Sexithiophenes Mediated by MM Quadruple Bonds: MM = Mo2, MoW, and W2 [J].

Alberding, Brian G. ;

Chisholm, Malcolm H. ;

Ghosh, Yagnaseni ;

Gustafson, Terry L. ;

Liu, Yao ;

Turro, Claudia .

INORGANIC CHEMISTRY, 2009, 48 (17) :8536-8543

[7] Direct observation of the luminescence from the 3δδ* excited state of Re2Cl2(p-OCH3form)4 [J].

Bradley, PM ;

Smith, LT ;

Eglin, JL ;

Turro, C .

INORGANIC CHEMISTRY, 2003, 42 (23) :7360-7362

[8] Early events in the photochemistry of aryl azides from femtosecond UV/vis spectroscopy and quantum chemical calculations [J].

Burdzinski, Gotard ;

Hackett, John C. ;

Wang, Jin ;

Gustafson, Terry L. ;

Hadad, Christopher M. ;

Platz, Matthew S. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (41) :13402-13411

[9] Observation of 1MLCT and 3MLCT excited states in quadruply bonded Mo2 and W2 complexes [J].

Byrnes, MJ ;

Chisholm, MH ;

Gallucci, JA ;

Liu, Y ;

Ramnauth, R ;

Turro, C .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (49) :17343-17352

[10] Studies of electronic coupling and mixed valency in metal-metal quadruply bonded complexes linked by dicarboxylate and closely related ligands [J].

Chisholm, Malcolm H. ;

Patmore, Nathan J. .

ACCOUNTS OF CHEMICAL RESEARCH, 2007, 40 (01) :19-27

← 1 2 3 4 →