DFT study of substitution effect on the geometry, IR spectra, spin state and energetic stability of the ferrocenes and their pentaphospholyl analogues

Gryaznova, T. V.; Katsyuba, Sergey A.; Milyukov, V. A.; Sinyashin, Оleg G.

doi:10.1016/j.jorganchem.2010.08.031

Cited by 53 publications

(77 citation statements)

References 74 publications

(31 reference statements)

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“…24 The band at ∼1454 cm −1 can be attributed to CH 2 scissoring of the aliphatic tails of the FcC 6 and in spectrum (b) also to C 6 , [25][26][27] while the bands at 1270-1350 cm −1 can be ascribed to C-C stretching in the aliphatic chains and in the ferrocene rings. 22,23 It can be easily noted that all of the features of the FcC 6 molecule are observed in all three spectra indicating that the molecules absorb intact on the surface. Furthermore, in PM-IRRAS spectra, the integrated band intensities of absorbed molecules is proportional to cos 2 θ , where θ is the angle between the average direction of the dipole moment and the surface normal.…”

Section: A Pm-irras Measurementsmentioning

confidence: 84%

“…Additionally an IR spectrum of (c) a KBr pellet of FcC 6 was acquired. The bands in the 1200-780 cm −1 region correspond to breathing and deformation of the methylenes of the ferrocene ring 22,23 and to CH 2 rocking and C-C stretching of the C 6 alkyl chain. 24 The band at ∼1454 cm −1 can be attributed to CH 2 scissoring of the aliphatic tails of the FcC 6 and in spectrum (b) also to C 6 , [25][26][27] while the bands at 1270-1350 cm −1 can be ascribed to C-C stretching in the aliphatic chains and in the ferrocene rings.…”

Section: A Pm-irras Measurementsmentioning

confidence: 99%

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Molecular and electronic structure of electroactive self-assembled monolayers

Leo

Llave

Scherlis

et al. 2013

The Journal of Chemical Physics

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Self-assembled monolayers (SAMs) containing electroactive functional groups are excellent model systems for the formation of electronic devices by self-assembly. In particular ferrocene-terminated alkanethiol SAMs have been extensively studied in the past. However, there are still open questions related with their electronic structure including the influence of the ferrocene group in the SAMinduced work function changes of the underlying metal. We have thus carried out a thorough experimental and theoretical investigation in order to determine the molecular and electronic structure of ferrocene-terminated alkanethiol SAMs on Au surfaces. In agreement with previous studies we found that the Fc-containing alkanethiol molecules adsorb forming a thiolate bond with the Au surface with a molecular geometry 30• tilted with respect to the surface normal. Measured surface coverages indicate the formation of a compact monolayer. We found for the first time that the ferrocene group has little influence on the observed work function decrease which is largely determined by the alkanethiol. Furthermore, the ferrocene moiety lies 14 Å above the metal surface covalently bonded to the alkanethiol SAM and its HOMO is located at −1.6 eV below the Fermi level. Our results provide new valuable insight into the molecular and electronic structure of electroactive SAMs which are of fundamental importance in the field of molecular electronics.

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Section: A Pm-irras Measurementsmentioning

confidence: 84%

Section: A Pm-irras Measurementsmentioning

confidence: 99%

Molecular and electronic structure of electroactive self-assembled monolayers

Leo

Llave

Scherlis

et al. 2013

The Journal of Chemical Physics

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“…The development of ferrocene study since its discovery in 1951 [1] has been well documented in recent articles such as Coriani et al [9], Roy et al [10], Gryaznova et al [11] and Bean et al [2]. It has been stated [11] that a staggered ferrocene structure of D 5d point group symmetry dominates experiments in the condensed phase [12e15], whereas the eclipsed structure of D 5h point group symmetry is found in the gas phase [16e18].…”

Section: Introductionmentioning

confidence: 99%

“…Density functional theory has been revealed as cost effective and accurate method to study electronic structures and properties of ferrocene [9,11]. It begins to recognize that the CpFeCp structure does not confine to the conventional FeeC "bonds" [2].…”

Section: Introductionmentioning

confidence: 99%

Differentiation of ferrocene D5d and D5h conformers using IR spectroscopy

Mohammadi

Ganesan

Chantler

et al. 2012

Journal of Organometallic Chemistry

103

161

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“…1) [1,2]. Specific bonding features, physical properties, and absorption behaviors of ferrocene, established various applications for this interesting compound in catalysis [3], molecular electronics and material science [4], bioelectronics [5], polymer chemistry [6], electrooptical [7], magnetic materials [8], biological research [9], biomedicinal chemistry [10], anticancer [11], and antineoplastic activity [12,13].…”

Section: Introductionmentioning

confidence: 99%

Ab initio studies of optoelectronic properties of fluorine-substituted ferrocene

2015

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Structural and optoelectronic properties of ferrocene and some derivatives (Fe C 10 X 10 , X = H, F) have been investigated by density functional theory. The full potential linearized augmented plane wave including generalized gradient approximation was used in this study. Since the ferrocene family has appealing photochemical and electrochemical properties, they have been extensively used in electronic and photonic industries. The current study accomplishes the electron density, density of states, and optical calculations. We have found that the optoelectronic properties of ferrocene change under substitution of hydrogen with fluorine. Band gaps of 2.72 and 0.92 eV were obtained for FeC 10 H 10 and FeC 10 F 10 , respectively. The band gap was obviously reduced for the full fluorine-substituted ferrocene compared with the unsubstituted one, which exhibited an increase in the charge transfer properties. Results of the optical calculations also confirm these findings.

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DFT study of substitution effect on the geometry, IR spectra, spin state and energetic stability of the ferrocenes and their pentaphospholyl analogues

Cited by 53 publications

References 74 publications

Molecular and electronic structure of electroactive self-assembled monolayers

Molecular and electronic structure of electroactive self-assembled monolayers

Differentiation of ferrocene D5d and D5h conformers using IR spectroscopy

Ab initio studies of optoelectronic properties of fluorine-substituted ferrocene

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