Electronic influences of bridging and chelating diimine ligand coordination in formamidinate-bridged Rh2 (II,II) dimers
Abstract
We report two new formamidinate-bridged Rh2II,II complexes, cis-[Rh2II,II(μ-DTolF)2(μ-np)2]2+ (3; DTolF = N,N'-di-p-tolylformamidinate; np = 1,8-naphthyridine) and cis-[Rh2II,II(μ-DTolF)2(κ2-dap)2]2+ (4; dap = 1,12-diazaperylene), were synthesized from cis-[Rh2II,II(μ-DTolF)2(CH3CN)6](BF4)2 (1), and their properties were compared to those of cis-[Rh2II,II(μ-DTolF)2(phen)2](BF4)2 (2). Density functional theory (DFT) and electrochemical analyses support the description of the highest occupied molecular orbitals (HOMOs) of 3 and 4 as possessing contributions from the metals and formamidinate bridging ligands, with Rh2/form character, and lowest unoccupied molecular orbitals (LUMOs) localized on the respective diimine ligand np and dap π* orbitals. Both 3 and 4 display strong, low energy Rh2/form → diimine(π*) metal/ligand-to-ligand charger transfer (1ML–LCT) transitions with maxima at 566 nm (ε = 3600 M-1 cm-1) for 3 and at 630 nm (ε = 2900 M-1 cm-1) for 4 in CH3CN. Time dependent-DFT (TD-DFT) calculations support these assignments. Finally, the ability of both the bridging np and chelating dap diimine ligands to produce strong absorption of these Rh2II,II complexes throughout the visible region is potentially useful for the development of new photocatalysts for H2 production and photochemotherapeutics.
- Authors:
-
- The Ohio State Univ., Columbus, OH (United States). Department of Chemistry and Biochemistry
- Texas A & M Univ., College Station, TX (United States). Department of Chemistry
- University of Houston, TX (United States). Department of Chemistry
- Publication Date:
- Research Org.:
- The Ohio State Univ., Columbus, OH (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1430205
- Alternate Identifier(s):
- OSTI ID: 1359777
- Grant/Contract Number:
- SC0010542; SC0010721
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Polyhedron
- Additional Journal Information:
- Journal Volume: 103; Journal Issue: PA; Journal ID: ISSN 0277-5387
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 14 SOLAR ENERGY; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Dirhodium; Naphthyridine; Diazaperylene; Light absorption; Electrochemistry
Citation Formats
White, Travis A., Dunbar, Kim R., Thummel, Randolph P., and Turro, Claudia. Electronic influences of bridging and chelating diimine ligand coordination in formamidinate-bridged Rh2 (II,II) dimers. United States: N. p., 2015.
Web. doi:10.1016/j.poly.2015.10.015.
White, Travis A., Dunbar, Kim R., Thummel, Randolph P., & Turro, Claudia. Electronic influences of bridging and chelating diimine ligand coordination in formamidinate-bridged Rh2 (II,II) dimers. United States. https://doi.org/10.1016/j.poly.2015.10.015
White, Travis A., Dunbar, Kim R., Thummel, Randolph P., and Turro, Claudia. Thu .
"Electronic influences of bridging and chelating diimine ligand coordination in formamidinate-bridged Rh2 (II,II) dimers". United States. https://doi.org/10.1016/j.poly.2015.10.015. https://www.osti.gov/servlets/purl/1430205.
@article{osti_1430205,
title = {Electronic influences of bridging and chelating diimine ligand coordination in formamidinate-bridged Rh2 (II,II) dimers},
author = {White, Travis A. and Dunbar, Kim R. and Thummel, Randolph P. and Turro, Claudia},
abstractNote = {We report two new formamidinate-bridged Rh2II,II complexes, cis-[Rh2II,II(μ-DTolF)2(μ-np)2]2+ (3; DTolF = N,N'-di-p-tolylformamidinate; np = 1,8-naphthyridine) and cis-[Rh2II,II(μ-DTolF)2(κ2-dap)2]2+ (4; dap = 1,12-diazaperylene), were synthesized from cis-[Rh2II,II(μ-DTolF)2(CH3CN)6](BF4)2 (1), and their properties were compared to those of cis-[Rh2II,II(μ-DTolF)2(phen)2](BF4)2 (2). Density functional theory (DFT) and electrochemical analyses support the description of the highest occupied molecular orbitals (HOMOs) of 3 and 4 as possessing contributions from the metals and formamidinate bridging ligands, with Rh2/form character, and lowest unoccupied molecular orbitals (LUMOs) localized on the respective diimine ligand np and dap π* orbitals. Both 3 and 4 display strong, low energy Rh2/form → diimine(π*) metal/ligand-to-ligand charger transfer (1ML–LCT) transitions with maxima at 566 nm (ε = 3600 M-1 cm-1) for 3 and at 630 nm (ε = 2900 M-1 cm-1) for 4 in CH3CN. Time dependent-DFT (TD-DFT) calculations support these assignments. Finally, the ability of both the bridging np and chelating dap diimine ligands to produce strong absorption of these Rh2II,II complexes throughout the visible region is potentially useful for the development of new photocatalysts for H2 production and photochemotherapeutics.},
doi = {10.1016/j.poly.2015.10.015},
journal = {Polyhedron},
number = PA,
volume = 103,
place = {United States},
year = {Thu Oct 22 00:00:00 EDT 2015},
month = {Thu Oct 22 00:00:00 EDT 2015}
}
Web of Science
Works referenced in this record:
Control and utilization of ruthenium and rhodium metal complex excited states for photoactivated cancer therapy
journal, January 2015
- Knoll, Jessica D.; Turro, Claudia
- Coordination Chemistry Reviews, Vol. 282-283
Photoinduced Ligand Exchange and Covalent DNA Binding by Two New Dirhodium Bis-Amidato Complexes
journal, October 2012
- Burya, Scott J.; Palmer, Alycia M.; Gallucci, Judith C.
- Inorganic Chemistry, Vol. 51, Issue 21
cis -[Rh 2 (μ-O 2 CCH 3 ) 2 (CH 3 CN) 6 ] 2+ as a Photoactivated Cisplatin Analog
journal, January 2006
- Lutterman, Daniel A.; Fu, Patty K. -L.; Turro, Claudia
- Journal of the American Chemical Society, Vol. 128, Issue 3
Photophysical Properties, DNA Photocleavage, and Photocytotoxicity of a Series of Dppn Dirhodium(II,II) Complexes
journal, June 2010
- Joyce, Lauren E.; Aguirre, J. Dafhne; Angeles-Boza, Alfredo M.
- Inorganic Chemistry, Vol. 49, Issue 12
Photoinduced interactions of two dirhodium complexes with d(GTCGAC) 2 probed by 2D NOESY
journal, January 2015
- Palmer, Alycia M.; Knoll, Jessica D.; Turro, Claudia
- Dalton Transactions, Vol. 44, Issue 8
Photoinduced Intercalation and Coordination of a Dirhodium Complex to DNA: Dual DNA Binding
journal, April 2014
- Palmer, Alycia M.; Burya, Scott J.; Gallucci, Judith C.
- ChemMedChem, Vol. 9, Issue 6
Directional charge transfer and highly reducing and oxidizing excited states of new dirhodium( ii , ii ) complexes: potential applications in solar energy conversion
journal, January 2014
- Li, Zhanyong; Leed, Nicholas A.; Dickson-Karn, Nicole M.
- Chem. Sci., Vol. 5, Issue 2
Optoelectronic Properties and Structural Effects of the Incremental Addition of Pyridyl Moieties on a Rhodium Dimer
journal, August 2014
- Chartrand, Daniel; Hanan, Garry S.
- The Journal of Physical Chemistry A, Vol. 118, Issue 45
Rhodium Amidinate Dimers as Structural and Functional Hubs for Multimetallic Assemblies
journal, December 2013
- Chartrand, Daniel; Hanan, Garry S.
- Inorganic Chemistry, Vol. 53, Issue 1
Photophysical Properties of MM Quadruply Bonded Complexes Supported by Carboxylate Ligands, MM = Mo 2 , MoW, or W 2
journal, November 2012
- Chisholm, Malcolm H.; Gustafson, Terry L.; Turro, Claudia
- Accounts of Chemical Research, Vol. 46, Issue 2
Electron delocalization in the S1 and T1 metal-to-ligand charge transfer states of trans-substituted metal quadruply bonded complexes
journal, April 2011
- Alberding, B. G.; Chisholm, M. H.; Gallucci, J. C.
- Proceedings of the National Academy of Sciences, Vol. 108, Issue 20
Synthesis, x-ray crystal structure, and electrochemical properties of the dirhodium(4+) complex Rh2(form)4 (form = N,N'-di-p-tolylformamidinate anion)
journal, July 1987
- Piraino, Pasquale; Bruno, Giuseppe; Lo Schiavo, Sandra
- Inorganic Chemistry, Vol. 26, Issue 14
Synthesis and characterization of dirhodium complexes with four N,N'-diphenylbenzamidine bridging ligands. Electrochemical generation and ESR properties of [Rh2(N2R2CR)4]n where R = Phenyl and n = 1 and -1
journal, November 1985
- Le, J. C.; Chavan, M. Y.; Chau, L. K.
- Journal of the American Chemical Society, Vol. 107, Issue 24
The influence of remote substituent in tetrakis(μ-N,N′-diarylformamidinato)–dirhodium(II) compounds. Part 7. Linear free energy relationships in dinuclear compounds
journal, January 2000
- Ren, Tong; Lin, Chun; Valente, Edward J.
- Inorganica Chimica Acta, Vol. 297, Issue 1-2
Photoinduced One-Electron Reduction of Alkyl Halides by Dirhodium(II,II) Tetraformamidinates and a Related Complex with Visible Light
journal, July 2005
- Lutterman, Daniel A.; Degtyareva, Natalya N.; Johnston, Dean H.
- Inorganic Chemistry, Vol. 44, Issue 15
Electrochemical, spectroscopic, and structural characterization of rhodium complexes Rh2(dpf)4, Rh2(dpf)4(CH3CN), and [Rh2(dpf)4(CH3CN)]ClO4, where dpf = N,N'-diphenylformamidinate(1-)
journal, January 1991
- Bear, John L.; Yao, C. L.; Lifsey, R. S.
- Inorganic Chemistry, Vol. 30, Issue 2
Synthesis and characterization of dirhodium(II,II) formamidinate complexes containing short-bite nitrogen ligands
journal, February 2003
- Tresoldi, Giuseppe; Lo Schiavo, Sandra; Nicolò, Francesco
- Inorganica Chimica Acta, Vol. 344
Dirhodium Formamidinate Compounds with Bidentate Nitrogen Chelating Ligands
journal, December 2003
- Chifotides, Helen T.; Catalan, Kemal V.; Dunbar, Kim R.
- Inorganic Chemistry, Vol. 42, Issue 26
Dirhodium(II) complexes with bi- and tri-dentate nitrogen-containing ligands
journal, January 1994
- Lo Schiavo, Sandra; Sinicropi, Maria S.; Tresoldi, Giuseppe
- Journal of the Chemical Society, Dalton Transactions, Issue 10
New Rh 2 (II,II) Architecture for the Catalytic Reduction of H +
journal, September 2015
- White, Travis A.; Witt, Suzanne E.; Li, Zhanyong
- Inorganic Chemistry, Vol. 54, Issue 20
Ruthenium(II) Complexes of 1,12-Diazaperylene and Their Interactions with DNA
journal, August 2005
- Chouai, Abdellatif; Wicke, Sara E.; Turro, Claudia
- Inorganic Chemistry, Vol. 44, Issue 17
A Novel Dirhodium Compound with Neutral, Bridging 9-Ethyladenine Ligands
journal, May 1997
- Catalan, Kemal V.; Mindiola, Daniel J.; Ward, Donald L.
- Inorganic Chemistry, Vol. 36, Issue 11
NMR Chemical Shifts of Trace Impurities: Common Laboratory Solvents, Organics, and Gases in Deuterated Solvents Relevant to the Organometallic Chemist
journal, May 2010
- Fulmer, Gregory R.; Miller, Alexander J. M.; Sherden, Nathaniel H.
- Organometallics, Vol. 29, Issue 9
Density-functional exchange-energy approximation with correct asymptotic behavior
journal, September 1988
- Becke, A. D.
- Physical Review A, Vol. 38, Issue 6
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
journal, January 1988
- Lee, Chengteh; Yang, Weitao; Parr, Robert G.
- Physical Review B, Vol. 37, Issue 2
Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993
- Becke, Axel D.
- The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
Energy-adjustedab initio pseudopotentials for the second and third row transition elements
journal, January 1990
- Andrae, D.; H�u�ermann, U.; Dolg, M.
- Theoretica Chimica Acta, Vol. 77, Issue 2
Electronic structure of phosphine adducts of tetrakis(carboxylato) dirhodium(II). Pronounced influence of axial ligands
journal, September 1981
- Bursten, Bruce E.; Cotton, F. Albert
- Inorganic Chemistry, Vol. 20, Issue 9
Absorption Spectrum and Solvatochromism of the [Ru(4,4‘-COOH-2,2‘-bpy) 2 (NCS) 2 ] Molecular Dye by Time Dependent Density Functional Theory
journal, April 2003
- Fantacci, Simona; De Angelis, Filippo; Selloni, Annabella
- Journal of the American Chemical Society, Vol. 125, Issue 14
Synthesis and reactivity of formamidinato rhodium(I) complexes
journal, January 1982
- Piraino, Pasquale; Tresoldi, Giuseppe; Faraone, Felice
- Journal of Organometallic Chemistry, Vol. 224, Issue 3
Insight into the Photoinduced Ligand Exchange Reaction Pathway of cis -[Rh 2 (μ-O 2 CCH 3 ) 2 (CH 3 CN) 6 ] 2+ with a DNA Model Chelate
journal, December 2011
- Chifotides, Helen T.; Lutterman, Daniel A.; Dunbar, Kim R.
- Inorganic Chemistry, Vol. 50, Issue 23
Theory of Stationary Electrode Polarography. Single Scan and Cyclic Methods Applied to Reversible, Irreversible, and Kinetic Systems.
journal, April 1964
- Nicholson, R. S.; Shain, Irving
- Analytical Chemistry, Vol. 36, Issue 4, p. 706-723
Ru(II) polypyridine complexes: photophysics, photochemistry, eletrochemistry, and chemiluminescence
journal, March 1988
- Juris, A.; Balzani, V.; Barigelletti, F.
- Coordination Chemistry Reviews, Vol. 84
Effect of Axial Coordination on the Electronic Structure and Biological Activity of Dirhodium(II,II) Complexes
journal, September 2007
- Aguirre, J. Dafhne; Lutterman, Daniel A.; Angeles-Boza, Alfredo M.
- Inorganic Chemistry, Vol. 46, Issue 18
Homologous Series of Redox-Active, Dinuclear Cations [M 2 (O 2 CCH 3 ) 2 (pynp) 2 ] 2+ (M = Mo, Ru, Rh) with the Bridging Ligand 2-(2-Pyridyl)-1,8-naphthyridine (pynp)
journal, March 2002
- Campos-Fernández, Cristian Saul; Thomson, Lisa M.; Galán-Mascarós, José Ramón
- Inorganic Chemistry, Vol. 41, Issue 6
Preparation and investigation of the spectral and electrochemical properties of mixed-ligand ruthenium(II) complexes containing 1,8-naphthyridines
journal, September 1977
- Staniewicz, Robert J.; Sympson, Robert F.; Hendricker, David G.
- Inorganic Chemistry, Vol. 16, Issue 9
Mono- and Dinuclear Ruthenium(II)-1,6,7,12-Tetraazaperylene Complexes of N , N′ -Dimethyl-2,11-diaza[3.3](2,6)-pyridinophane: Mono- and Dinuclear Ruthenium(II)-1,6,7,12-Tetraazaperylene Complexes
journal, August 2012
- Brietzke, Thomas; Mickler, Wulfhard; Kelling, Alexandra
- European Journal of Inorganic Chemistry, Vol. 2012, Issue 29
Works referencing / citing this record:
The crystal structure of 1,12-diazaperylene, C18H10N2
journal, November 2019
- Kirste, Matthias; Brietzke, Thomas; Holdt, Hans-Jürgen
- Zeitschrift für Kristallographie - New Crystal Structures, Vol. 234, Issue 6
Electrospray mass spectrometry and molecular modeling study of formation and stability of silver complexes with diazaperylene and bisisoquinoline
journal, March 2018
- Starke, Ines; Koch, Andreas; Kammer, Stefan
- Journal of Mass Spectrometry, Vol. 53, Issue 5
The crystal structure of 1,12-diazaperylene, C₁₈H₁₀N₂
text, January 2019
- Kirste, Matthias; Brietzke, Thomas; Holdt, Hans-Jürgen
- Universität Potsdam