A fast time-resolved infrared spectroscopic investigation into the nature of the lowest excited state and excimer formation in PtII diimine cyanides

Marina K. Kuimova; Michael Ya Mel'nikov; Julia A. Weinstein; Michael W. George

doi:10.1039/b202511f

A fast time-resolved infrared spectroscopic investigation into the nature of the lowest excited state and excimer formation in Pt^II diimine cyanides

Marina K. Kuimova, Michael Ya Mel'nikov, Julia A. Weinstein, Michael W. George

Research output: Journal Publication › Article › peer-review

18 Citations (Scopus)

Abstract

Time-resolved infrared spectroscopy (TRIR) has been used to probe the nature of the lowest excited state of [Pt^II(dpphen)(CN)₂] (dpphen = 4,7-diphenyl-1,10-phenanthroline) both in fluid solution at room temperature and in a glass at 77 K. The positions of the v(CN) bands in [Pt^II(dpphen)(CN)₂] are only slightly (less than 5 cm^-1) shifted upon formation of the excited state, thus supporting their assignment as the π-π* intraligand state. At 77 K [Pt^II(dpphen)(CN)₂] has a highly structured luminescence with a lifetime of 170 μs, which is also characteristic of a π-π* excited state. In contrast, the lowest excited state of [Ru(bpy)₂(CN)₂] has MLCT character in both fluid solution at ambient temperature and at 77 K as shown by a large positive shift of v(CN) relative to the ground state. Also we have monitored the monomer-excimer equilibrium of [Pt^II(dpphen)(CN)₂] in fluid solution using the ns-TRIR technique.

Original language	English
Pages (from-to)	2857-2861
Number of pages	5
Journal	Journal of the Chemical Society. Dalton Transactions
Volume	14
DOIs	https://doi.org/10.1039/b202511f
Publication status	Published - 2002
Externally published	Yes

ASJC Scopus subject areas

General Chemistry

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title = "A fast time-resolved infrared spectroscopic investigation into the nature of the lowest excited state and excimer formation in PtII diimine cyanides",

abstract = "Time-resolved infrared spectroscopy (TRIR) has been used to probe the nature of the lowest excited state of [PtII(dpphen)(CN)2] (dpphen = 4,7-diphenyl-1,10-phenanthroline) both in fluid solution at room temperature and in a glass at 77 K. The positions of the v(CN) bands in [PtII(dpphen)(CN)2] are only slightly (less than 5 cm-1) shifted upon formation of the excited state, thus supporting their assignment as the π-π* intraligand state. At 77 K [PtII(dpphen)(CN)2] has a highly structured luminescence with a lifetime of 170 μs, which is also characteristic of a π-π* excited state. In contrast, the lowest excited state of [Ru(bpy)2(CN)2] has MLCT character in both fluid solution at ambient temperature and at 77 K as shown by a large positive shift of v(CN) relative to the ground state. Also we have monitored the monomer-excimer equilibrium of [PtII(dpphen)(CN)2] in fluid solution using the ns-TRIR technique.",

author = "Kuimova, {Marina K.} and Mel'nikov, {Michael Ya} and Weinstein, {Julia A.} and George, {Michael W.}",

year = "2002",

doi = "10.1039/b202511f",

language = "English",

volume = "14",

pages = "2857--2861",

journal = "Journal of the Chemical Society. Dalton Transactions",

issn = "1470-479X",

publisher = "Royal Society of Chemistry",

}

A fast time-resolved infrared spectroscopic investigation into the nature of the lowest excited state and excimer formation in Pt^II diimine cyanides. / Kuimova, Marina K.; Mel'nikov, Michael Ya; Weinstein, Julia A. et al.
In: Journal of the Chemical Society. Dalton Transactions, Vol. 14, 2002, p. 2857-2861.

Research output: Journal Publication › Article › peer-review

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T1 - A fast time-resolved infrared spectroscopic investigation into the nature of the lowest excited state and excimer formation in PtII diimine cyanides

AU - Kuimova, Marina K.

AU - Mel'nikov, Michael Ya

AU - Weinstein, Julia A.

AU - George, Michael W.

PY - 2002

Y1 - 2002

N2 - Time-resolved infrared spectroscopy (TRIR) has been used to probe the nature of the lowest excited state of [PtII(dpphen)(CN)2] (dpphen = 4,7-diphenyl-1,10-phenanthroline) both in fluid solution at room temperature and in a glass at 77 K. The positions of the v(CN) bands in [PtII(dpphen)(CN)2] are only slightly (less than 5 cm-1) shifted upon formation of the excited state, thus supporting their assignment as the π-π* intraligand state. At 77 K [PtII(dpphen)(CN)2] has a highly structured luminescence with a lifetime of 170 μs, which is also characteristic of a π-π* excited state. In contrast, the lowest excited state of [Ru(bpy)2(CN)2] has MLCT character in both fluid solution at ambient temperature and at 77 K as shown by a large positive shift of v(CN) relative to the ground state. Also we have monitored the monomer-excimer equilibrium of [PtII(dpphen)(CN)2] in fluid solution using the ns-TRIR technique.

AB - Time-resolved infrared spectroscopy (TRIR) has been used to probe the nature of the lowest excited state of [PtII(dpphen)(CN)2] (dpphen = 4,7-diphenyl-1,10-phenanthroline) both in fluid solution at room temperature and in a glass at 77 K. The positions of the v(CN) bands in [PtII(dpphen)(CN)2] are only slightly (less than 5 cm-1) shifted upon formation of the excited state, thus supporting their assignment as the π-π* intraligand state. At 77 K [PtII(dpphen)(CN)2] has a highly structured luminescence with a lifetime of 170 μs, which is also characteristic of a π-π* excited state. In contrast, the lowest excited state of [Ru(bpy)2(CN)2] has MLCT character in both fluid solution at ambient temperature and at 77 K as shown by a large positive shift of v(CN) relative to the ground state. Also we have monitored the monomer-excimer equilibrium of [PtII(dpphen)(CN)2] in fluid solution using the ns-TRIR technique.

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A fast time-resolved infrared spectroscopic investigation into the nature of the lowest excited state and excimer formation in Pt^II diimine cyanides

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