Theoretical studies on metal-metal interaction, excited states, and spectroscopic properties of binuclear Au-Au, Au-Rh, and Rh-Rh complexes with diphosphine ligands: Buildup of complexity from monomers to dimers

Qing Jiang Pan; Xin Zhou; Yuan Ru Guo; Hong Gang Fu; Hong Xing Zhang

doi:10.1021/ic801687w

Theoretical studies on metal-metal interaction, excited states, and spectroscopic properties of binuclear Au-Au, Au-Rh, and Rh-Rh complexes with diphosphine ligands: Buildup of complexity from monomers to dimers

Qing Jiang Pan
, Xin Zhou
, Yuan Ru Guo
, Hong Gang Fu
, Hong Xing Zhang

Heilongjiang University
Northeast Forestry University
Jilin University

Research output: Contribution to journal › Article › peer-review

24 Scopus citations

Abstract

To understand their photocatalytic activity and application in luminescent materials, a series of gold and rhodium phosphine complexes (mononuclear [Au ^l(PH ₃) ₂] ⁺ (1) and [Rh ^l(CNH) ₂(PH ₃) ₂] ⁺ (2); homobinuclear [Au ^l ₂(PH ₂CH ₂PH ₂) ₂] ²⁺(3)and[Rh ^l ₂(CNH) 4(PH ₂CH ₂PH ₂) ₂] ²⁺(4) ;heterobinuclearíAu ^lRh ^l(CNH) ₂(PH ₂CH ₂PH ₂) ₂] ²⁺(5),[Au ^lRh ^l(CNH) ₂(PH ₂NHPH ₂) ₂CI ₂] (6), and [Au ^lRh ^l(CNH) ₂(PH ₂NHPH ₂) ₂] ²⁺ (7); and oxidized derivatives [Au ^llRh ^llCNH) ₂(PH ₂CH ₂PH ₂) ₂] ⁴⁺ (8), [Au ^llRh ^ll(CNH) ₂(PH ₂NHPH ₂) ₂CI ₃] ⁺ (9), and [Au ^llRh ^ll(CNH) ₂(PH ₂NHPH ₂) ₂] ⁴⁺ (10)) were investigated using ab initio methods and density functional theory. With the use of the MP2 method, the M-M' distances in 3-7 were estimated to be in the range of 2.76-3.02 Å, implying the existence of weak metal-metal interaction. This is further evident in the stretching frequencies and bond orders of M-M'. The two-electron oxidation from 5-7 to their respective partners 8-10 was shown to mainly occur in the gold-rhodium centers. Experimental absorption spectra were well reproduced by our time-dependent density functional theory calculations. The metal-metal interaction results in a large shift of d _z ²→ p _z transition absorptions in binuclear complexes relative to mononuclear analogues and concomitantly produces a low-lying excited state that is responsible for increasing visible-light photocatalytic activities. Upon excitation, the metal-centered transition and the metal-to-metal charge transfer strengthen the metal-metal interaction in triplet excited states for 3-6, while the promotion of electrons into the σ*(d _z ²) orbital weakens the interaction in 9.

Original language	English
Pages (from-to)	2844-2854
Number of pages	11
Journal	Inorganic Chemistry
Volume	48
Issue number	7
DOIs	https://doi.org/10.1021/ic801687w
State	Published - 2009
Externally published	Yes

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@article{e97f263631634e3e8875adebc0aad80a,

title = "Theoretical studies on metal-metal interaction, excited states, and spectroscopic properties of binuclear Au-Au, Au-Rh, and Rh-Rh complexes with diphosphine ligands: Buildup of complexity from monomers to dimers",

abstract = "To understand their photocatalytic activity and application in luminescent materials, a series of gold and rhodium phosphine complexes (mononuclear [Au l(PH 3) 2] + (1) and [Rh l(CNH) 2(PH 3) 2] + (2); homobinuclear [Au l 2(PH 2CH 2PH 2) 2] 2+(3)and[Rh l 2(CNH) 4(PH 2CH 2PH 2) 2] 2+(4) ;heterobinuclear{\'i}Au lRh l(CNH) 2(PH 2CH 2PH 2) 2] 2+(5),[Au lRh l(CNH) 2(PH 2NHPH 2) 2CI 2] (6), and [Au lRh l(CNH) 2(PH 2NHPH 2) 2] 2+ (7); and oxidized derivatives [Au llRh llCNH) 2(PH 2CH 2PH 2) 2] 4+ (8), [Au llRh ll(CNH) 2(PH 2NHPH 2) 2CI 3] + (9), and [Au llRh ll(CNH) 2(PH 2NHPH 2) 2] 4+ (10)) were investigated using ab initio methods and density functional theory. With the use of the MP2 method, the M-M' distances in 3-7 were estimated to be in the range of 2.76-3.02 {\AA}, implying the existence of weak metal-metal interaction. This is further evident in the stretching frequencies and bond orders of M-M'. The two-electron oxidation from 5-7 to their respective partners 8-10 was shown to mainly occur in the gold-rhodium centers. Experimental absorption spectra were well reproduced by our time-dependent density functional theory calculations. The metal-metal interaction results in a large shift of d z 2→ p z transition absorptions in binuclear complexes relative to mononuclear analogues and concomitantly produces a low-lying excited state that is responsible for increasing visible-light photocatalytic activities. Upon excitation, the metal-centered transition and the metal-to-metal charge transfer strengthen the metal-metal interaction in triplet excited states for 3-6, while the promotion of electrons into the σ*(d z 2) orbital weakens the interaction in 9.",

author = "Pan, \{Qing Jiang\} and Xin Zhou and Guo, \{Yuan Ru\} and Fu, \{Hong Gang\} and Zhang, \{Hong Xing\}",

year = "2009",

doi = "10.1021/ic801687w",

language = "英语",

volume = "48",

pages = "2844--2854",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "7",

}

Theoretical studies on metal-metal interaction, excited states, and spectroscopic properties of binuclear Au-Au, Au-Rh, and Rh-Rh complexes with diphosphine ligands: Buildup of complexity from monomers to dimers. / Pan, Qing Jiang; Zhou, Xin; Guo, Yuan Ru et al.
In: Inorganic Chemistry, Vol. 48, No. 7, 2009, p. 2844-2854.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Theoretical studies on metal-metal interaction, excited states, and spectroscopic properties of binuclear Au-Au, Au-Rh, and Rh-Rh complexes with diphosphine ligands

T2 - Buildup of complexity from monomers to dimers

AU - Pan, Qing Jiang

AU - Zhou, Xin

AU - Guo, Yuan Ru

AU - Fu, Hong Gang

AU - Zhang, Hong Xing

PY - 2009

Y1 - 2009

N2 - To understand their photocatalytic activity and application in luminescent materials, a series of gold and rhodium phosphine complexes (mononuclear [Au l(PH 3) 2] + (1) and [Rh l(CNH) 2(PH 3) 2] + (2); homobinuclear [Au l 2(PH 2CH 2PH 2) 2] 2+(3)and[Rh l 2(CNH) 4(PH 2CH 2PH 2) 2] 2+(4) ;heterobinuclearíAu lRh l(CNH) 2(PH 2CH 2PH 2) 2] 2+(5),[Au lRh l(CNH) 2(PH 2NHPH 2) 2CI 2] (6), and [Au lRh l(CNH) 2(PH 2NHPH 2) 2] 2+ (7); and oxidized derivatives [Au llRh llCNH) 2(PH 2CH 2PH 2) 2] 4+ (8), [Au llRh ll(CNH) 2(PH 2NHPH 2) 2CI 3] + (9), and [Au llRh ll(CNH) 2(PH 2NHPH 2) 2] 4+ (10)) were investigated using ab initio methods and density functional theory. With the use of the MP2 method, the M-M' distances in 3-7 were estimated to be in the range of 2.76-3.02 Å, implying the existence of weak metal-metal interaction. This is further evident in the stretching frequencies and bond orders of M-M'. The two-electron oxidation from 5-7 to their respective partners 8-10 was shown to mainly occur in the gold-rhodium centers. Experimental absorption spectra were well reproduced by our time-dependent density functional theory calculations. The metal-metal interaction results in a large shift of d z 2→ p z transition absorptions in binuclear complexes relative to mononuclear analogues and concomitantly produces a low-lying excited state that is responsible for increasing visible-light photocatalytic activities. Upon excitation, the metal-centered transition and the metal-to-metal charge transfer strengthen the metal-metal interaction in triplet excited states for 3-6, while the promotion of electrons into the σ*(d z 2) orbital weakens the interaction in 9.

AB - To understand their photocatalytic activity and application in luminescent materials, a series of gold and rhodium phosphine complexes (mononuclear [Au l(PH 3) 2] + (1) and [Rh l(CNH) 2(PH 3) 2] + (2); homobinuclear [Au l 2(PH 2CH 2PH 2) 2] 2+(3)and[Rh l 2(CNH) 4(PH 2CH 2PH 2) 2] 2+(4) ;heterobinuclearíAu lRh l(CNH) 2(PH 2CH 2PH 2) 2] 2+(5),[Au lRh l(CNH) 2(PH 2NHPH 2) 2CI 2] (6), and [Au lRh l(CNH) 2(PH 2NHPH 2) 2] 2+ (7); and oxidized derivatives [Au llRh llCNH) 2(PH 2CH 2PH 2) 2] 4+ (8), [Au llRh ll(CNH) 2(PH 2NHPH 2) 2CI 3] + (9), and [Au llRh ll(CNH) 2(PH 2NHPH 2) 2] 4+ (10)) were investigated using ab initio methods and density functional theory. With the use of the MP2 method, the M-M' distances in 3-7 were estimated to be in the range of 2.76-3.02 Å, implying the existence of weak metal-metal interaction. This is further evident in the stretching frequencies and bond orders of M-M'. The two-electron oxidation from 5-7 to their respective partners 8-10 was shown to mainly occur in the gold-rhodium centers. Experimental absorption spectra were well reproduced by our time-dependent density functional theory calculations. The metal-metal interaction results in a large shift of d z 2→ p z transition absorptions in binuclear complexes relative to mononuclear analogues and concomitantly produces a low-lying excited state that is responsible for increasing visible-light photocatalytic activities. Upon excitation, the metal-centered transition and the metal-to-metal charge transfer strengthen the metal-metal interaction in triplet excited states for 3-6, while the promotion of electrons into the σ*(d z 2) orbital weakens the interaction in 9.

UR - https://www.scopus.com/pages/publications/64549094956

U2 - 10.1021/ic801687w

DO - 10.1021/ic801687w

M3 - 文章

C2 - 19281182

AN - SCOPUS:64549094956

SN - 0020-1669

VL - 48

SP - 2844

EP - 2854

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 7

ER -

Theoretical studies on metal-metal interaction, excited states, and spectroscopic properties of binuclear Au-Au, Au-Rh, and Rh-Rh complexes with diphosphine ligands: Buildup of complexity from monomers to dimers

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