Ab initio studies of optoelectronic properties of fluorine-substituted ferrocene

Aliabad, H. A. Rahnamaye; Tayebee, Reza; Khalili, Mey

doi:10.1007/s11164-015-2242-8

Cited by 9 publications

(3 citation statements)

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“…[16][17][18] Despite these interests and the role of metallocenes in many of these areas of fundamental and applied interest, few polyfluorometallocenes have been described, and structureproperty relationships are limited in scope. [19][20][21] Concerning η 6 coordination compounds, a few arene-vanadium, 22 chromium [23][24][25][26][27][28] and -rhodium 29,30 complexes with up to six fluorine atoms on the aromatic ring have been reported. However, η 5 -coordination complexes are limited to a handful of examples (Figure 1).…”

Section: Introductionmentioning

confidence: 99%

From ferrocene to 1,2,3,4,5-pentafluoroferrocene: halogen effect on the properties of metallocene

et al. 2021

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Section: Introductionmentioning

confidence: 99%

From ferrocene to 1,2,3,4,5-pentafluoroferrocene: halogen effect on the properties of metallocene

et al. 2021

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“…This reduction is slightly smaller than for the literature‐known compounds in the benzene series (0.1 eV/SPh). The common practice of associating the HOMO–LUMO gap with the “optical band gap” (see above) clearly cannot applied here, and, therefore, once again, one should always keep in mind that spectra “measure differences in state energies, not orbital energies” …”

Section: Methodsmentioning

confidence: 99%

Ferrocenes with a Persulfurated Cyclopentadienyl Ring: Synthesis, Structural Studies, and Optoelectronic Properties

Blockhaus

Klein-Heßling

Zehetmaier

et al. 2019

Chemistry A European J

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Persulfurateda renes are af ascinating class of functional molecules with aw ider ange of potentiala pplications. Ferrocenes are also am ultifaceted class of aromatic compounds that can easily be finetuned for an enormous variety of desired properties. Ac ombinationo f both substancec lasses might yield an even wider field of applications. Herein, we describe the synthesis of two ferrocenesw ith one persulfurated cyclopentadienyl ring [C 5 (SR) 5 ], with R = Me or Ph, together with their crystal structures, optical, and electrochemical properties. Both crystal structures show significant intramolecular sulfuriron interactions as well as weak intermoleculars ulfurcontacts. Cyclovoltammetry of the [C 5 (SPh) 5 ]c ompound shows ah igho xidationp otentialo f6 51 mV vs. FcH/FcH + .Persulfurated arenes still remain an underexploited field of chemistry,d espite their highly interesting physical organic properties and their numerous possible applications, ranging from ion-selectivem embranes over organic conductors and ferromagnets to cation sensors andl iquid crystals. [1] This statement made by M. Gingras in af ascinatingr eview article in this journal more than 10 years ago is still valid. There have been, however,s everali nteresting additions to this field, particularly with extended aromatic systems. Per(arylthio)corannulenes and -coronenes have found potential applicationa sp hotovoltaic devices [2] and for molecular electronics. [3] Substituted hexakis(phenylthio)benzenes showeds trong phosphorescence in the solid state with the potential of OLED applications. [4] Dendrimersw ith a[ C 6 (SAr) 6 ]c ore, so-called" molecular asterisks" have been used as multifunctional ligandsf or the preparation of luminescents ensors and asymmetric metal catalysis. [5] The interesting electronic properties sharedb yt his compound class are mainly due to the fact that "phenylthio substituents attached to aromatic cores result in ar eduction of the HOMO-LUMOg ap", [1, 2a] "primarily due to LUMO stabilization". [6] Upon addition of SPh groups ab athochromic shift of the longest wavelength absorption by 10-15 nm is observed together with an increaseofthereductionpotential by 0.1 V. [2b] Metallocenes are another very important group of aromatics with very interestinge lectronic properties. However,w hile quite af ew metal-freep ersulfurated arenes have been studied, there seem to be no reports of persulfuratedferrocenes. The fivefolds ymmetry of metallocenes would create as tructural motifr arely found with thioether-based "moleculara sterisks" (Scheme 1). [7] While the syntheses of persulfurated cyclopentadienyl anions[ C 5 (SR) 5 ] À (R = Me, Ph) was already reported in the 1980s, [8] attempts to prepare metallocenes from them via reactions with metal halidesm et with failure. However,t he complexes[ C 5 (SMe) 5 ]ML n (ML n = Mn(CO) 3 ,R uCp*) could be obtainedv ia post-functionalization of an already coordinated cyclopentadienyl ring. [9,10] Transfer of this syntheticp rotocol using perhalogenatedo rp ermercurated ferroce...

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“…In addition to the homofluoroferrocenes mentioned, some derivatives including decafluoroferrocene were the subject of theoretical calculations. 15…”

Section: Scheme 3 Fluorination Of 2-pyridylferrocene (11) 14mentioning

confidence: 99%

Haloferrocenes: Syntheses and Selected Reactions

Butenschön

2018

Synthesis

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Although haloferrocenes constitute important starting materials for many ferrocene-derived products with importance in a variety of fields such as materials science, medicinal chemistry and catalysis, only relatively few haloferrocenes out of the large number of possible examples have been prepared so far. The first part of this review summarizes the syntheses of all the homo- and heterohaloferrocenes known up to date. The second part summarizes typical reactions of haloferrocenes, namely lithiation followed by trapping with an electrophile, copper-mediated halogen substitution, coupling with formation of diferrocenyl derivatives, ortho-lithiation followed by trapping with an electrophile, palladium-catalyzed coupling reactions and finally miscellaneous reactions.1 Introduction2 Homohaloferrocenes2.1 Fluoroferrocenes2.2 Chloroferrocenes2.3 Bromoferrocenes2.4 Iodoferrocenes3 Heterohaloferrocenes4 Selected Reactions of Haloferrocenes4.1 Lithiation Followed by Trapping with an Electrophile4.2 Copper-Mediated Halogen Substitution4.3 Coupling with Formation of Diferrocenyl Derivatives4.4 ortho-Lithiation of Haloferrocenes4.5 Palladium-Catalyzed Reactions of Haloferrocenes4.6 Miscellaneous Reactions of Haloferrocenes5 Conclusions

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Ab initio studies of optoelectronic properties of fluorine-substituted ferrocene

Cited by 9 publications

References 58 publications

From ferrocene to 1,2,3,4,5-pentafluoroferrocene: halogen effect on the properties of metallocene

From ferrocene to 1,2,3,4,5-pentafluoroferrocene: halogen effect on the properties of metallocene

Ferrocenes with a Persulfurated Cyclopentadienyl Ring: Synthesis, Structural Studies, and Optoelectronic Properties

Haloferrocenes: Syntheses and Selected Reactions

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