Theoretical Studies on the Structures and Spectroscopic Properties of N-Heterocyclic Carbene-pyridine-based Ruthenium Sensitizers†

doi:10.7503/cjcu20140060

Abstract

Abstract:

Using bidentate N-heterocyclic carbene-pyridine ligands in substitution for two thiocyanates of the N749, a series of novel thiocyanate-free cyclometalated ruthenium polypyridine complexes(1—4) was designed. These complexes were studied theoretically using density functional theory(DFT) and time-dependent density functional theory(TD-DFT) techniques to explore their geometry structures, electronic structures and the spectral properties. The calculations indicate that the lowest-energy absorption of complexes 1—4 in CH₃CN solution is calculated at around 800 nm, arise from the MLCT/LLCT transition.

Key words: N-Heterocyclic carbene-pyridine, Ruthenium, Electron absorption, Density functional theory, Time dependent-density functional theory

CLC Number:

O641

TrendMD:

XIA Xiquan, ZHANG Hui, ZHANG Guiling. Theoretical Studies on the Structures and Spectroscopic Properties of N-Heterocyclic Carbene-pyridine-based Ruthenium Sensitizers^†[J]. Chem. J. Chinese Universities, 2014, 35(5): 1000.

Figures/Tables 7

References 31

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Parameter	1	2	3	4	N749	Expt.^[28]
Ru—N1/nm	0.2098	0.2106	0.2099	0.2101	0.2062	0.2090
Ru—N2/nm	0.2022	0.2024	0.2018	0.2026	0.1937	0.1936
Ru—N3/nm	0.2097	0.2095	0.2098	0.2100	0.2062
Ru—N4/nm	0.2066	0.2040	0.2030	0.2040	0.2040	0.2032
Ru—N5/nm	0.2108	0.2102	0.2117	0.2101	0.2040
Ru—C1(N6)/nm	0.2006	0.2029	0.2006	0.2019	0.2073	0.2052
N1—C2/nm	0.1361	0.1360	0.1360	0.1359	0.1358
N1—C3/nm	0.1387	0.1387	0.1387	0.1386	0.1389
N2—C4/nm	0.1367	0.1365	0.1367	0.1364	0.1379
N5—C5/nm	0.1363	0.1363	0.1364	0.1364
N5—C6/nm	0.1375	0.1371	0.1372	0.1369
N1—Ru—N2/(°)	78.8	78.7	78.9	78.8	80.5	81.1
N3—Ru—N2/(°)	78.8	78.8	78.8	78.7	80.5
N1—Ru—N3/(°)	157.5	157.6	157.6	157.4	161.1	161.6
N5—Ru—C1/(°)	77.6	77.9	77.2	77.6

Parameter	1	2	3	4	N749	Expt.^[28]
Ru—N1/nm	0.2098	0.2106	0.2099	0.2101	0.2062	0.2090
Ru—N2/nm	0.2022	0.2024	0.2018	0.2026	0.1937	0.1936
Ru—N3/nm	0.2097	0.2095	0.2098	0.2100	0.2062
Ru—N4/nm	0.2066	0.2040	0.2030	0.2040	0.2040	0.2032
Ru—N5/nm	0.2108	0.2102	0.2117	0.2101	0.2040
Ru—C1(N6)/nm	0.2006	0.2029	0.2006	0.2019	0.2073	0.2052
N1—C2/nm	0.1361	0.1360	0.1360	0.1359	0.1358
N1—C3/nm	0.1387	0.1387	0.1387	0.1386	0.1389
N2—C4/nm	0.1367	0.1365	0.1367	0.1364	0.1379
N5—C5/nm	0.1363	0.1363	0.1364	0.1364
N5—C6/nm	0.1375	0.1371	0.1372	0.1369
N1—Ru—N2/(°)	78.8	78.7	78.9	78.8	80.5	81.1
N3—Ru—N2/(°)	78.8	78.8	78.8	78.7	80.5
N1—Ru—N3/(°)	157.5	157.6	157.6	157.4	161.1	161.6
N5—Ru—C1/(°)	77.6	77.9	77.2	77.6

MO	Energy/eV	Compositions(%)				Assignment of orbital
MO	Energy/eV	Ru		tcterpy	NHC-py	NCS
LUMO+7	-1.35159	1	0	98	0	π^*(NHC-py)
LUMO+4	-2.12167	8	2	91	1	π^*(NHC-py)
LUMO+3	-2.57447	1	99	1	0	π^*(tcterpy)
LUMO+2	-2.80957	1	99	0	0	π^*(tcterpy)
LUMO+1	-3.08523	5	94	0	0	π^*(tcterpy)
LUMO	-3.52687	7	92	0	1	π^*(tcterpy)
HOMO	-5.83602	32	5	4	58	d(Ru)-π^*(NCS)
HOMO-1	-5.89943	24	6	1	68	d(Ru)-π^*(NCS)
HOMO-2	-6.55658	55	7	38	1	d(Ru)-π^*(NHC-py)
HOMO-3	-6.87142	36	13	9	41	d(Ru)-π^*(NCS)
HOMO-4	-7.09863	48	15	2	35	d(Ru)-π^*(NCS)
HOMO-5	-7.24748	3	3	95	1	π(NHC-py)
HOMO-6	-7.69565	2	95	1	1	π(tcterpy)
HOMO-7	-7.86817	18	4	76	1	π(NHC-py)
HOMO-8	-8.17756	0	0	100	0	π(NHC-py)
HOMO-9	-8.49675	2	96	0	1	π(tcterpy)
HOMO-10	-8.59227	1	89	10	0	p(COOH)

MO	Energy/eV	Compositions(%)				Assignment of orbital
MO	Energy/eV	Ru		tcterpy	NHC-py	NCS
LUMO+7	-1.35159	1	0	98	0	π^*(NHC-py)
LUMO+4	-2.12167	8	2	91	1	π^*(NHC-py)
LUMO+3	-2.57447	1	99	1	0	π^*(tcterpy)
LUMO+2	-2.80957	1	99	0	0	π^*(tcterpy)
LUMO+1	-3.08523	5	94	0	0	π^*(tcterpy)
LUMO	-3.52687	7	92	0	1	π^*(tcterpy)
HOMO	-5.83602	32	5	4	58	d(Ru)-π^*(NCS)
HOMO-1	-5.89943	24	6	1	68	d(Ru)-π^*(NCS)
HOMO-2	-6.55658	55	7	38	1	d(Ru)-π^*(NHC-py)
HOMO-3	-6.87142	36	13	9	41	d(Ru)-π^*(NCS)
HOMO-4	-7.09863	48	15	2	35	d(Ru)-π^*(NCS)
HOMO-5	-7.24748	3	3	95	1	π(NHC-py)
HOMO-6	-7.69565	2	95	1	1	π(tcterpy)
HOMO-7	-7.86817	18	4	76	1	π(NHC-py)
HOMO-8	-8.17756	0	0	100	0	π(NHC-py)
HOMO-9	-8.49675	2	96	0	1	π(tcterpy)
HOMO-10	-8.59227	1	89	10	0	p(COOH)

Complex	State	Config(\|CI\| coef.)		λ/nm(E/eV)		Oscillator strength		Assignment
1	A ¹A	H→L(0.69)		729(1.70)		0.0329		MLCT/LLCT
	B ¹A	H-1→L(0.61)		610(2.03)		0.0310		MLCT/LLCT
	C ¹A	H-2→L(0.69)		585(2.12)		0.0028		MLCT/LLCT
	D ¹A	H-1→L+1(0.65)		521(2.38)		0.0665		MLCT/LLCT
	E ¹A	H→L+2(0.68)		477(2.60)		0.1015		MLCT/LLCT
	F ¹A	H-3→L+1(0.63)		370(3.35)		0.1452		MLCT/LLCT
	G ¹A	H-6→L(0.54)		336(3.69)		0.4367		π(tcterpy)→π^*(tcterpy)
		H-3→L+2(0.39)						MLCT/LLCT
	H ¹A	H-4→L+4(0.45)		266(4.66)		0.3790		π(NHC-py)→π^*(NHC-py)
		H-2→L+7(0.28)						MLCT/LLCT
2	A ¹A	H→L(0.69)		769(1.61)		0.0309		MLCT/LLCT
	B ¹A	H-1→L(0.66)		660(1.88)		0.0156		MLCT/LLCT
	C ¹A	H-2→L(0.69)		594(2.09)		0.0017		MLCT/LLCT
	D ¹A	H-1→L+1(0.69)		546(2.27)		0.0326		MLCT/LLCT
	E ¹A	H→L+2(0.69)		495(2.50)		0.0803		MLCT/LLCT
	F ¹A	H-3→L+1(0.59)		380(3.26)		0.1104		MLCT/LLCT
	G ¹A	H-8→L(0.52)		339(3.66)		0.2986		π(tcterpy)→π^*(tcterpy)
	H ¹A	H-5→L+4(0.52)		280(4.43)		0.0955		π(NHC-py)→π^*(NHC-py)
3	A ¹A	H→L(0.69)		773(1.60)		0.0259		MLCT/LLCT
	B ¹A	H-1→L(0.68)		683(1.82)		0.0259		MLCT/LLCT
	C ¹A	H-1→L+1(0.70)		565(2.20)		0.0266		MLCT/LLCT
	D ¹A	H-2→L(0.69)		557(2.23)		0.0018		MLCT/LLCT
	E ¹A	H→L+2(0.69)		480(2.58)		0.0342		MLCT/LLCT
	F ¹A	H-3→L+1(0.61)		378(3.28)		0.1665		MLCT/LLCT
	G ¹A	H-6→L(0.59)		340(3.65)		0.4973		π(tcterpy)→π^*(tcterpy)
		H-3→L+2(0.31)						MLCT/LLCT
	H ¹A	H-5→L+4(0.52)		277(4.48)		0.3485		π(NHC-py)→π^*(NHC-py)
		H-2→L+7(0.37)						MLCT
4	A ¹A	H→L(0.70)		777(1.60)		0.0243		MLCT/LLCT
	B ¹A	H-1→L(0.69)		693(1.79)		0.0136		MLCT/LLCT
	C ¹A	H→L+1(0.67)		564(2.20)		0.0165		MLCT/LLCT
	D ¹A	H→L+2(0.69)		498(2.49)		0.0511		MLCT/LLCT
Complex	State	Config(\|CI\| coef.)	λ/nm(E/eV)		Oscillator strength		Assignment		Expt.^[12] /nm
4	E ¹A	H-3→L+1(0.61)	382(3.24)		0.1711		MLCT/LLCT
	F ¹A	H-6→L(0.59)	340(3.64)		0.5049		π(tcterpy)→π^*(tcterpy)
	G ¹A	H-5→L+4(0.58)	275(4.50)		0.0790		π(NHC-py)→π^*(NHC-py)
N749	A ¹A'	H→L+1(0.65)	859(1.44)		0.0409		MLCT/LLCT
	B ¹A'	H→L+2(0.57)	686(1.80)		0.1182		MLCT/LLCT		625
	C ¹A″	H-6→L(0.66)	513(2.42)		0.0516		MLCT/LLCT		556
	D ¹A'	H-6→L+2(0.64)	393(3.16)		0.1586		MLCT/LLCT		429
	E ¹A'	H-9→L(0.64)	334(3.72)		0.2683		π(tcterpy)→π^*(tcterpy)		344,330