Electronic spectra of the tetraphenylcyclobutadienecyclopentadienylnickel(II) cation and radical

Miller, John R.; Havlas, Zdenek; Trujillo, Marianela; Rempala, Pawel; Kirby, James P.; Noll, Bruce C.; Michl, Josef

doi:10.1021/acs.jpca.6b00648

Title: Electronic spectra of the tetraphenylcyclobutadienecyclopentadienylnickel(II) cation and radical

Abstract

In this study, properties of the tetraphenylcyclobutadienecyclopentadienylnickel(II) cation 1 and its tetra-o-fluoro derivative 1a have been measured and calculated. The B3LYP/TZP optimized geometry of the free cation 1 agrees with a single-crystal X-ray diffraction structure except that in the crystal one of the phenyl substituents is strongly twisted to permit a close-packing interaction of two of its hydrogens with a nearby BF^–₄ anion. The low-energy parts of the solution electronic absorption and magnetic circular dichroism (MCD) spectra of 1 and 1a have been interpreted by comparison with TD-DFT (B3LYP/TZP) results. Reduction or pulse radiolysis lead to a neutral 19-electron radical, whose visible absorption and MCD spectra have been recorded and interpreted as well. The reduction is facilitated by ~0.1 V upon going from 1 to 1a

Authors:

Peter R. Craig; Miller, John R. ^[1]; Havlas, Zdenek ^[2]; Trujillo, Marianela ^[3]; Rempala, Pawel ^[3]; Kirby, James P. ^[1]; Noll, Bruce C. ^[3]; Michl, Josef ^[4]

Brookhaven National Lab. (BNL), Upton, NY (United States)
Academy of Science of the Czech Republic, Prague (Czech Republic)
Univ. of Colorado, Boulder, CO (United States)
Univ. of Colorado, Boulder, CO (United States); Academy of Science of the Czech Republic, Prague (Czech Republic)

Publication Date:: Mon May 02 00:00:00 EDT 2016

Research Org.:: Brookhaven National Lab. (BNL), Upton, NY (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1255730

Report Number(s):: BNL-112249-2016-JA
Journal ID: ISSN 1089-5639; R&D Project: CO-04; KC0301

Grant/Contract Number:: SC0012704

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

Additional Journal Information:: Journal Volume: 120; Journal Issue: 20; Journal ID: ISSN 1089-5639

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 14 SOLAR ENERGY; exciton transport; triplet; conjugated polymers; molecular wires; exciton diffusion; Laser Electron Accelerator Facility (LEAF)

Citation Formats


                    Peter R. Craig, Miller, John R., Havlas, Zdenek, Trujillo, Marianela, Rempala, Pawel, Kirby, James P., Noll, Bruce C., and Michl, Josef. Electronic spectra of the tetraphenylcyclobutadienecyclopentadienylnickel(II) cation and radical.  United States: N. p., 2016. 
Web.  doi:10.1021/acs.jpca.6b00648.

Copy to clipboard


                    Peter R. Craig, Miller, John R., Havlas, Zdenek, Trujillo, Marianela, Rempala, Pawel, Kirby, James P., Noll, Bruce C., & Michl, Josef. Electronic spectra of the tetraphenylcyclobutadienecyclopentadienylnickel(II) cation and radical.  United States.  https://doi.org/10.1021/acs.jpca.6b00648

Copy to clipboard


                    Peter R. Craig, Miller, John R., Havlas, Zdenek, Trujillo, Marianela, Rempala, Pawel, Kirby, James P., Noll, Bruce C., and Michl, Josef. Mon .  
"Electronic spectra of the tetraphenylcyclobutadienecyclopentadienylnickel(II) cation and radical".  United States.  https://doi.org/10.1021/acs.jpca.6b00648.  https://www.osti.gov/servlets/purl/1255730.

Copy to clipboard


                    
@article{osti_1255730,

  title        = {Electronic spectra of the tetraphenylcyclobutadienecyclopentadienylnickel(II) cation and radical},

  author       = {Peter R. Craig and Miller, John R. and Havlas, Zdenek and Trujillo, Marianela and Rempala, Pawel and Kirby, James P. and Noll, Bruce C. and Michl, Josef},

  abstractNote = {In this study, properties of the tetraphenylcyclobutadienecyclopentadienylnickel(II) cation 1 and its tetra-o-fluoro derivative 1a have been measured and calculated. The B3LYP/TZP optimized geometry of the free cation 1 agrees with a single-crystal X-ray diffraction structure except that in the crystal one of the phenyl substituents is strongly twisted to permit a close-packing interaction of two of its hydrogens with a nearby BF–4 anion. The low-energy parts of the solution electronic absorption and magnetic circular dichroism (MCD) spectra of 1 and 1a have been interpreted by comparison with TD-DFT (B3LYP/TZP) results. Reduction or pulse radiolysis lead to a neutral 19-electron radical, whose visible absorption and MCD spectra have been recorded and interpreted as well. The reduction is facilitated by ~0.1 V upon going from 1 to 1a},

  doi          = {10.1021/acs.jpca.6b00648},

  journal      = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},

  number       = 20,

  volume       = 120,

  place        = {United States},

  year         = {Mon May 02 00:00:00 EDT 2016},

  month        = {Mon May 02 00:00:00 EDT 2016}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

https://doi.org/10.1021/acs.jpca.6b00648

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 2 works

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

Works referenced in this record:

Cyclobutadienemetal complexes
journal, October 1977

Efraty, Avi.
Chemical Reviews, Vol. 77, Issue 5
DOI: 10.1021/cr60309a003

Toward a Square-Grid Polymer: Synthesis and Structure of Pedestal-Mounted Tetragonal Star Connectors, C ₄ R ₄ −Co−C ₅ Y ₅
journal, July 1997

Harrison, Robin M.; Brotin, Thierry; Noll, Bruce C.
Organometallics, Vol. 16, Issue 15
DOI: 10.1021/om9700730

Toward a Square Grid Polymer: Electrochemistry of Tentacled Tetragonal Star Connectors, C ₄ R ₄ −Co−C ₅ (HgY) ₅ , on Mercury
journal, December 1998

Brotin, Thierry; Pospíšil, Lubomír; Fiedler, Jan
The Journal of Physical Chemistry B, Vol. 102, Issue 49
DOI: 10.1021/jp983242i

Tetraarylcyclobutadienecyclopentadienylcobalt Complexes: Synthesis, Electronic Spectra, Magnetic Circular Dichroism, Linear Dichroism, and TD DFT Calculations
journal, June 2014

Kottas, Gregg S.; Brotin, Thierry; Schwab, Peter F. H.
Organometallics, Vol. 33, Issue 13
DOI: 10.1021/om400403j

Cyclobutadiene-Metal Complexes. IV. ¹ (π-Cyclopentadienyl) (π-tetraphenylcyclobutadiene) palladium Halides and Related Complexes
journal, February 1965

Maitlis, P. M.; Efraty, A.; Games, M. L.
Journal of the American Chemical Society, Vol. 87, Issue 4
DOI: 10.1021/ja01082a007

Cyclobutadiene-metal complexes XII. Syntheses and some reactions ofpara-substituted-(tetraphenylcyclobutadiene)palladium halides
journal, February 1971

Pollock, D. F.; Maitlis, P. M.
Journal of Organometallic Chemistry, Vol. 26, Issue 3
DOI: 10.1016/S0022-328X(00)82623-6

Elektronenüberschuß-Komplexe von Cobalt und Nickel mit Cyclobutadien-Liganden: Synthese, Cyclovoltammetrie und Reaktivität
journal, July 1992

Herberich, Gerhard E.; Klein, Wolfram; Kölle, Ulrich
Chemische Berichte, Vol. 125, Issue 7
DOI: 10.1002/cber.19921250713

Reduktion von (Cyclobutadien)(cyclopentadienyl)- und (1,5-Cyclooctadien)- (cyclopentadienyl)nickel-Kationen
journal, February 1990

Kölle, Ulrich; Ting-Zhen, Ding; Keller, Hubert
Chemische Berichte, Vol. 123, Issue 2
DOI: 10.1002/cber.19901230202

Magnetic circular dichroism of cyclic .pi.-electron systems. 1. Algebraic solution of the perimeter model for the A and B terms of high-symmetry systems with a (4N + 2)-electron [n]annulene perimeter
journal, October 1978

Michl, Josef
Journal of the American Chemical Society, Vol. 100, Issue 22
DOI: 10.1021/ja00490a001

Observation of the Predicted Negative Faraday A MCD Term in a Cyclobutadiene Dianion
journal, June 2001

Ishii, Kazuyuki; Kobayashi, Nagao; Matsuo, Tsukasa
Journal of the American Chemical Society, Vol. 123, Issue 22
DOI: 10.1021/ja004285r

Optimized Slater-type basis sets for the elements 1-118
journal, May 2003

Van Lenthe, E.; Baerends, E. J.
Journal of Computational Chemistry, Vol. 24, Issue 9
DOI: 10.1002/jcc.10255

Works referencing / citing this record:

Magnetic circular dichroism of an unaromatic planar [8]annulene
journal, May 2018

Wen, Jin; Uto, Takayuki; Chalupský, Jakub
Journal of Physical Organic Chemistry, Vol. 31, Issue 8
DOI: 10.1002/poc.3854

Similar Records in DOE PAGES and OSTI.GOV collections:

Toward Designed Singlet Fission: Electronic States and Photophysics of 1,3-Diphenylisobenzofuran

Journal Article Schwerin, A F ; Miller, J ; Johnson, J C ; ... - Journal of Physical Chemistry A

Single crystal molecular structure and solution photophysical properties are reported for 1,3-diphenylisobenzofuran (1), of interest as a model compound in studies of singlet fission. For the ground state of 1 and of its radical cation (1{sup +{sm_bullet}}) and anion (1{sup -{sm_bullet}}), we report the UV-visible absorption spectra, and for neutral 1, also the magnetic circular dichroism (MCD) and the decomposition of the absorption spectrum into purely polarized components, deduced from fluorescence polarization. These results were used to identify a series of singlet excited states. For the first excited singlet and triplet states of 1, the transient visible absorption spectra, S{submore »« less
Photochemical, electrochemical, and chemical formulation of the. pi. -cation-radical species of magnesium phthalocyanine. Analysis of the absorption and MCD spectra of (MgPc( minus 1)) ter dot +

Journal Article Ough, E ; Gasyna, Z ; Stillman, M J - Inorganic Chemistry; (United States)

Photochemical, electrochemical, and chemical methods have been used to form the ring-oxidized, {pi}-cation-radical species of magnesium phtalocyanine (MgPc({minus}1)){sup {center dot}+}. Photooxidation of MgPc({minus}2) was carried out by excitation with visible region light into the Phthalocyanine Q band at 670 nm, using carbon tetrabromide as an irreversible electron acceptor. The radical cation was also formed by controlled potential coulometry at the first oxidation potential (+0.70 V vs SCE) of MgPc({minus}2) and by chemical oxidation with nitric acid. Absorption and magnetic circular dichroism (MCD) spectra are reported between 250 and 850 nm for ((L){sub n}MgPc({minus}1)){sup {center dot}+} (n = 1,2) {pi}-cation-radical species,more »« less
https://doi.org/10.1021/ic00010a016
Phthalocyanine. pi. -cation-radical species: photochemical and electrochemical preparation of (ZnPc(-1))/sup. +/ in solution

Journal Article Nyokong, T ; Gasyna, Z ; Stillman, M J - Inorg. Chem.; (United States)

The ..pi..-cation-radical species of ZnPc, (ZnPc(-1))/sup .+/ (Pc = phthalocyanine), has been formed quantitatively as a stable product in solution following photochemical reactions with visible-region light in the presence of electron acceptors. The photolyses were carried out by excitation into the phthalocyanine's Q band (lambda > 580 nm), with carbon tetrabromide as an irreversible electron acceptor. The neutral parent species could be regenerated following photooxidation by the addition of sodium dithionite. Cyclic voltammetry of neutral ZnPcL species identified the ring oxidation potentials; for ZnPc(py) and ZnPc(im) (py = pyridine; im = imidazole). In dimethylacetamide, there is one oxidation couple atmore »« less
https://doi.org/10.1021/ic00251a012
Spectroscopic investigation of the electronic and excited state properties of para-substituted tetraphenyl porphyrins and their electrochemically generated ions

Journal Article Hanna, Lauren ; Movsesian, Edgar ; Orozco, Miguel ; ... - Spectrochimica Acta. Part A. Molecular and Biomolecular Spectroscopy

Porphyrins play pivotal roles in many crucial biological processes including photosynthesis. However, there is still a knowledge gap in understanding electronic and excited state implications associated with functionalization of the porphyrin ring system. These effects can have electrochemical and spectroscopic signatures that reveal the complex nature of these somewhat minor substitutions, beyond simple inductive or electronic effect correlations. To obtain a deeper insight into the influences of porphyrin functionalization, four free-base, meso-substituted porphyrins: tetraphenyl porphyrin (TPP), tetra(4-hydroxyphenyl) porphyrin (THPP), tetra(4-carboxyphenyl) porphyrin (TCPP), and tetra(4-nitrophenyl) porphyrin (TNPP), were synthesized, characterized, and investigated. The influence of various substituents, (-hydroxy,-carboxy, and -nitro) inmore »« less
https://doi.org/10.1016/j.saa.2022.121300

Full Text Available
SO2-Binding Properties of Cationic η6,η1-NCN-Pincer Arene Ruthenium Platinum Complexes: Spectroscopic and Theoretical Studies

Journal Article Bonnet, Sylvestre A ; Van Lenthe, Joop H ; van Dam, Hubertus JJ ; ... - Dalton Transactions, 40(11):2542-2548

The SO2-binding properties of a series of η6,η1-NCN-pincer ruthenium platinum complexes have been studied by both UV-visible spectroscopy, and theoretical calculations. When an electronwithdrawing [Ru(C5R5)]+ fragment (R = H or Me) is η6-coordinated to the phenyl ring of the NCNpincer platinum fragment (cf. [2]+ and [3]+, see scheme 1), the characteristic orange coloration (pointing to η1- SO2 binding to Pt) of a solution of the parent NCN-pincer platinum complex 1 in dichloromethane upon SO2-bubbling is not observed. However, when the ruthenium center is η6- coordinated to a phenyl substituent linked in para-position to the carbon-to-platinum bond, i.e. complex [4]+, themore »« less
https://doi.org/10.1039/C0DT01437K

Similar Records
Related Works
dataset (1)

Title: Electronic spectra of the tetraphenylcyclobutadienecyclopentadienylnickel(II) cation and radical

Abstract

Citation Formats

Cyclobutadienemetal complexes journal, October 1977

Toward a Square-Grid Polymer: Synthesis and Structure of Pedestal-Mounted Tetragonal Star Connectors, C 4 R 4 −Co−C 5 Y 5 journal, July 1997

Toward a Square Grid Polymer: Electrochemistry of Tentacled Tetragonal Star Connectors, C 4 R 4 −Co−C 5 (HgY) 5 , on Mercury journal, December 1998

Tetraarylcyclobutadienecyclopentadienylcobalt Complexes: Synthesis, Electronic Spectra, Magnetic Circular Dichroism, Linear Dichroism, and TD DFT Calculations journal, June 2014

Cyclobutadiene-Metal Complexes. IV. 1 (π-Cyclopentadienyl) (π-tetraphenylcyclobutadiene) palladium Halides and Related Complexes journal, February 1965

Cyclobutadiene-metal complexes XII. Syntheses and some reactions ofpara-substituted-(tetraphenylcyclobutadiene)palladium halides journal, February 1971

Elektronenüberschuß-Komplexe von Cobalt und Nickel mit Cyclobutadien-Liganden: Synthese, Cyclovoltammetrie und Reaktivität journal, July 1992

Reduktion von (Cyclobutadien)(cyclopentadienyl)- und (1,5-Cyclooctadien)- (cyclopentadienyl)nickel-Kationen journal, February 1990

Magnetic circular dichroism of cyclic .pi.-electron systems. 1. Algebraic solution of the perimeter model for the A and B terms of high-symmetry systems with a (4N + 2)-electron [n]annulene perimeter journal, October 1978

Observation of the Predicted Negative Faraday A MCD Term in a Cyclobutadiene Dianion journal, June 2001

Optimized Slater-type basis sets for the elements 1-118 journal, May 2003

Magnetic circular dichroism of an unaromatic planar [8]annulene journal, May 2018

Cyclobutadienemetal complexes
journal, October 1977

Toward a Square-Grid Polymer: Synthesis and Structure of Pedestal-Mounted Tetragonal Star Connectors, C ₄ R ₄ −Co−C ₅ Y ₅
journal, July 1997

Toward a Square Grid Polymer: Electrochemistry of Tentacled Tetragonal Star Connectors, C ₄ R ₄ −Co−C ₅ (HgY) ₅ , on Mercury
journal, December 1998

Tetraarylcyclobutadienecyclopentadienylcobalt Complexes: Synthesis, Electronic Spectra, Magnetic Circular Dichroism, Linear Dichroism, and TD DFT Calculations
journal, June 2014

Cyclobutadiene-Metal Complexes. IV. ¹ (π-Cyclopentadienyl) (π-tetraphenylcyclobutadiene) palladium Halides and Related Complexes
journal, February 1965

Cyclobutadiene-metal complexes XII. Syntheses and some reactions ofpara-substituted-(tetraphenylcyclobutadiene)palladium halides
journal, February 1971

Elektronenüberschuß-Komplexe von Cobalt und Nickel mit Cyclobutadien-Liganden: Synthese, Cyclovoltammetrie und Reaktivität
journal, July 1992

Reduktion von (Cyclobutadien)(cyclopentadienyl)- und (1,5-Cyclooctadien)- (cyclopentadienyl)nickel-Kationen
journal, February 1990

Magnetic circular dichroism of cyclic .pi.-electron systems. 1. Algebraic solution of the perimeter model for the A and B terms of high-symmetry systems with a (4N + 2)-electron [n]annulene perimeter
journal, October 1978

Observation of the Predicted Negative Faraday A MCD Term in a Cyclobutadiene Dianion
journal, June 2001

Optimized Slater-type basis sets for the elements 1-118
journal, May 2003

Magnetic circular dichroism of an unaromatic planar [8]annulene
journal, May 2018