publication . Article . 2017

Energetics of Saddling versus Ruffling in Metalloporphyrins: Unusual Ruffled Dodecasubstituted Porphyrins

Jeanet Conradie; Abhik Ghosh;
Open Access English
  • Published: 01 Oct 2017 Journal: ACS Omega, volume 2, issue 10, pages 6,708-6,714 (issn: 2470-1343, Copyright policy)
  • Publisher: American Chemical Society
  • Country: Norway
Abstract
Source at <a href=http://doi.org/10.1021/acsomega.7b01004> http://doi.org/10.1021/acsomega.7b01004 </a>. Presented herein is a first major density functional theory (BP86/D3/STO-TZ2P) survey of the energetics of saddling versus ruffling for a wide range of dodecasubstituted metalloporphyrins with M = Ni, Cu, Zn, Pd, and Pt. For the majority of X<sub>8</sub>TPP (i.e., β-octasubstituted-meso-tetraphenylporphyrin), the calculations indicated a clear preference for the saddled conformation, consistent with a large body of experimental data. The preference for the saddled conformation relative to the ruffled conformation was found to vary from about ∼0.3–0.4 eV for M...
Persistent Identifiers
Subjects
free text keywords: VDP::Matematikk og Naturvitenskap: 400::Kjemi: 440::Teoretisk kjemi, kvantekjemi: 444, VDP::Mathematics and natural science: 400::Chemistry: 440::Theoretical chemistry, quantum chemistry: 444, Article, lcsh:Chemistry, lcsh:QD1-999, Crystallography, Density functional theory, Energetics, Chemistry, Stereochemistry
Funded by
EC| PROMOTE
Project
PROMOTE
The molecular mechanism of the reversible switch between cell proliferation and migration. The regulatory function of the ERK pathway and ERK pathway scaffold RACK1
  • Funder: European Commission (EC)
  • Project Code: 231086
  • Funding stream: FP7 | SP3 | PEOPLE
,
EC| EPOS
Project
EPOS
European Plate Observing System
  • Funder: European Commission (EC)
  • Project Code: 262229
  • Funding stream: FP7 | SP4 | INFRA
Communities
EPOSEPOS Projects: EPOS
59 references, page 1 of 4

Shelnutt J. A.; Song X.-Z.; Ma J.-G.; Jia S.-L.; Jentzen W.; Medforth C. J.; Medforth C. J.Nonplanar Porphyrins and Their Significance in Proteins. Chem. Soc. Rev.1998, 27, 31–42. 10.1039/A827031Z. [OpenAIRE] [DOI]

Golubchikov O. A.; Pukhovskaya S. G.; Kuvshinova E. M.Structures and Properties of Spatially Distorted Porphyrins. Russ. Chem. Rev.2005, 74, 249–264. 10.1070/RC2005v074n03ABEH000925. [OpenAIRE] [DOI]

Kleingardner J. G.; Bren K. L.Acc. Chem. Res.2015, 48, 1845–1852. 10.1021/acs.accounts.5b00106.26083801 [OpenAIRE] [PubMed] [DOI]

Brennan T. D.; Scheidt W. R.; Shelnutt J. A.J. Am. Chem. Soc.1988, 110, 3919 10.1021/ja00220a033. [OpenAIRE] [DOI]

Meyer E. F.Jr.Acta Crystallogr., Sect. B: Struct. Crystallogr. Cryst. Chem.1972, 28, 2162 10.1107/S0567740872005722. [DOI]

Jia S.-L.; Jentzen W.; Shang M.; Song X.-Z.; Ma J.-G.; Scheidt W. R.; Shelnutt J. A.Axial Coordination and Conformational Heterogeneity of Nickel(II) Tetraphenylporphyrin Complexes with Nitrogenous Bases. Inorg. Chem.1998, 37, 4402–4412. 10.1021/ic980289+.11670577 [OpenAIRE] [PubMed] [DOI]

Kozlowski P. M.; Rush T. S.III; Jarzecki A. A.; Zgierski M.; Chase B.; Piffat C. A.; Ye B.-H.; Li Z.-Y.; Pulay P.; Spiro T. G.DFT-SQM Force Field for Nickel Porphine: Intrinsic Ruffling. J. Phys. Chem. A 1999, 103, 1357–1366. 10.1021/jp9819700. [OpenAIRE] [DOI]

Rush T. S.III; Kozlowski P. M.; Piffat C. A.; Kumble R.; Zgierski M.; Spiro T. G.Computational Modeling of Metalloporphyrin Structure and Vibrational Spectra: Porphyrin Ruffling in NiTPP. J. Phys. Chem. B 2000, 104, 5020–5034. 10.1021/jp000266s. [OpenAIRE] [DOI]

Nakamura M.Electronic Structures of Highly Deformed Iron(III) Porphyrin Complexes. Coord. Chem. Rev.2006, 250, 2271–2294. 10.1016/j.ccr.2006.03.001. [OpenAIRE] [DOI]

Senge M. O.; Bischoff I.; Nelson N. Y.; Smith K. M.Synthesis, reactivity and structural chemistry of 5,10,15,20-tetraalkylporphyrins. J. Porphyrins Phthalocyanines 1999, 3, 99–116. 10.1002/(SICI)1099-1409(199902)3:2<99::AID-JPP109>3.0.CO;2-6. [DOI]

Ema T.; Senge M. O.; Nelson N. Y.; Ogoshi H.; Smith K. M.5,10,15,20-Tetra-tert-butylporphyrin and Its Remarkable Reactivity in the 5- and 15-Positions. Angew. Chem., Int. Ed.1994, 33, 1879–1881. (CSD reference code HETDAL)10.1002/anie.19941879 1. [OpenAIRE] [DOI]

Senge M. O.; Ema T.; Smith K. M.Crystal structure of a remarkably ruffled nonplanar porphyrin (pyridine)[5,10,15,20-tetra(tert-butyl)porphyrinato]zinc(II). J. Chem. Soc., Chem. Commun.1995, 733–734. (CSD reference code ZIJDAX)10.1039/c39950000733. [OpenAIRE] [DOI]

Barkigia K. M.; Nurco D. J.; Renner M. W.; Melamed D.; Smith K. M.; Fajer J.Multiconformational Surfaces in Porphyrins: Previews into Excited-State Landscapes. J. Phys. Chem. B 1998, 102, 322–326. 10.1021/jp973013g. [OpenAIRE] [DOI]

Nurco D. J.; Medforth C. J.; Forsyth T. P.; Olmstead M. M.; Smith K. M.Conformational Flexibil ity in Dodecasubstituted Porphyrins. J. Am. Chem. Soc.1996, 118, 10918–10919. (CSD reference code TEZXEB, TEZXIF)10.1021/ja962164e. [OpenAIRE] [DOI]

Drain C. M.; Kirmaier C.; Medforth C. J.; Nurco D. J.; Smith K. M.; Holten D.Dynamic Photophysical Properties of Conformationally Distorted Nickel Porphyrins. 1. Nickel(II) Dodecaphenylporphyrin. J. Phys. Chem.1996, 100, 11984–11993. 10.1021/jp960735j. [OpenAIRE] [DOI]

59 references, page 1 of 4
Any information missing or wrong?Report an Issue