Synthesis of 12-Substituted 1-Carba-closo-dodecaborate Anions and First Hyperpolarizability of the 12-C7H6+-CB11H11- Ylide

Grüner, Bohumı́r; Janoušek, Zbyněk; King, Benjamin T.; Woodford, Jeffrey N.; Wang, C. H.; Všetečka, Václav; Michl, Josef

doi:10.1021/ja982368q

Cited by 107 publications

(70 citation statements)

References 34 publications

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“…20 Previous studies of carborane derivatives for NLO purposes have been reported. 21 The crystal The π orbital overlap between phenyl group and tangential cluster orbitals has been invoked to explain the cage C-C lengthening in aryl-ortho-carborane derivatives. 24,25 This was further explored by ab initio RHF/6-31G* and MP2/6-31G* calculational studies on 1-phenylortho-carborane and other aryl-carboranes in order to probe the orientational preferences of aryl groups attached to the carbon atoms of ortho-carborane.…”

Section: Structural Aspectsmentioning

confidence: 99%

Sulfur, tin and gold derivatives of 1-(2′-pyridyl)-ortho-carborane, 1-R-2-X-1,2-C₂B₁₀H₁₀(R = 2′-pyridyl, X = SH, SnMe₃or AuPPh₃)

et al. 2004

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Citation for published item:f ts novD eF F nd poxD wFeF nd ri ertD FqF nd row rdD tFeFuF nd uivek¤ sD F nd v rom ineD eF nd ill np¤ ¤ D F nd i£ n sD gF nd deD uF @PHHRA 9 ulfurD tin nd gold deriv tives of IE@PEpyridylAEorthoE r or neD IE EPE EIDPEgPfIHrIH @ a PEpyridylD a rD nweQ or eu hQAF9D h lton tr ns tionsFD PHHR @PPAF ppF QVPPEQVPVF Further information on publisher's website: Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-pro t purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. AbstractReaction

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Section: Structural Aspectsmentioning

confidence: 99%

Sulfur, tin and gold derivatives of 1-(2′-pyridyl)-ortho-carborane, 1-R-2-X-1,2-C₂B₁₀H₁₀(R = 2′-pyridyl, X = SH, SnMe₃or AuPPh₃)

et al. 2004

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“…The strong bonds between carborane and metal combined with high electronic delocalization provide great stability and diverse applications of these compounds [3,7] in medicine [9][10][11][12] and materials sciences [13][14][15][16][17][18][19][20] [16]. In addition, Grüner et al [18] obtained a derivative [12-C 7 H + 6 -CB 11 H − 11 ] with β ten times larger than p-nitroaniline (9.2 × 10 −30 cm 5 /esu) [24]. Recently, we studied the role played by substituent effects on NLO properties of dicarba-closo-dodecarboranes isomers 1,2-(ortho-), 1,7-(meta-) and 1,12-(para-) C 2 B 10 H 12 [8].…”

Section: Introductionmentioning

confidence: 99%

“…Studies in this area involving carboranes include synthesis of novel compounds [14,18] and NLO properties' calculations [5,8,[15][16][17]21,28]. For example, a new class of dodecarboranes ([B 12 H 11 -C 2 B 10 H 11 ] 2− ) with potential application as NLO materials was proposed through ab initio calculations (1)…”

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confidence: 99%

Theoretical study of nonlinear optical properties of cobalt bis (dicarbollide) derivatives: the effect of substituents

Junqueira

Sato

2015

Theor Chem Acc

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interesting feature of the boron-based cages, due to high electronic and thermal stability, delocalized structures and easy functionalization, is the potential application in nonlinear optics (NLO) [3,5,21]. Generally, molecules with NLO applications are systems with acceptor and donor electron groups in its extremities (push-pull type), high values of first-order hyperpolarizability (β) and permanent dipole moment (d). The second-order responses can be enhanced by increasing the electronic asymmetry or the conjugation length between the extremity groups [22,23]. Besides, the structure must be non-centrosymmetric, and the molecules must present absorption at wavelength greater than 400 nm for second harmonic generation (SHG), to avoid re-absorption of the converted light [24]. The energy (E) of a molecular system under an external electric field F can be written as Eq. (1), where E(0) is the energy of the system in the absence of an external field, and F i are the components of the applied field [25]:The dipole moment (d), the linear polarizability (α), and the first-and second-order hyperpolarizabilities (β and γ) play a significant role mainly in the study of NLO properties [24,26,27].The NLO behavior of icosahedral carboranes has been investigated for more than 20 years [14]. Studies in this area involving carboranes include synthesis of novel compounds [14,18] and NLO properties' calculations [5,8,[15][16][17]21,28]. For example, a new class of dodecarboranes ([B 12 H 11 -C 2 B 10 H 11 ] 2− ) with potential application as NLO materials was proposed through ab initio calculations (1)In the present work, molecular first-order hyperpolarizability (β tot ) and dipole moment (d) are obtained at B3LYP/6-31G(d,p) level of theory by coupled perturbed Hartree-Fock method within the static approach. The investigated molecules are a series of substituted cobalt bis (dicarbollide) derivatives: Hydrogens bonded to the two carbon atoms are replaced by acceptor and donor electron substituents. Correlations between the Hammett electronic parameters of the substituents and the molecular properties are tested. Among them, the named push-pull compounds produced the largest calculated values of β tot and d. The UV-Vis spectra are reported for all studied compounds.

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“…The family of closo-carboranes (C 2 B n H n+2 , n=4-10) is characterized by high thermal stability [10], [11], [12] and these systems have been regarded as three-dimensional aromatic analogues of benzene [13]. However, very little attention has been paid to the study of carboranes as potential NLO-materials ([14], [15], [16], [17]) z and the hyperpolarizability of donor/acceptor-substituted 6-vertex carboranes has not been investigated. Earlier studies on 10-and 12-vertex boranes and carboranes [17] have suggested that these molecules may be promising candidates in the design of NLO-e®ective compounds.…”

Section: Introductionmentioning

confidence: 99%

Hyperpolarizability of 6-vertex carboranes quantum chemical study

Suponitsky

Timofeeva

2003

Open Chemistry

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Structure and molecular rst hyperpolarizability ( ) of nitro-amino-substituted 6-vertex 1,6-carboranes are investigated by means of DFT calculations. The results obtained have revealed that the relative orientation of substituents with respect to the carborane cage in®uences bond lengths distribution in the cage, which leads to signi cant changes in the values of hyperpolarizabilities. Calculations with di¬erent basis sets have demonstrated that the value of is not signi cantly a¬ected by the choice of basis set. The calculated data shows that hyperpolarizability of carborane molecules substituted for carbon atoms is lower than when substituted for boron atoms. For latter molecule, the value of is of the same order as that of para-nitroaniline molecule.

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Synthesis of 12-Substituted 1-Carba-closo-dodecaborate Anions and First Hyperpolarizability of the 12-C₇H₆⁺-CB₁₁H₁₁^- Ylide

Cited by 107 publications

References 34 publications

Sulfur, tin and gold derivatives of 1-(2′-pyridyl)-ortho-carborane, 1-R-2-X-1,2-C₂B₁₀H₁₀(R = 2′-pyridyl, X = SH, SnMe₃or AuPPh₃)

Sulfur, tin and gold derivatives of 1-(2′-pyridyl)-ortho-carborane, 1-R-2-X-1,2-C₂B₁₀H₁₀(R = 2′-pyridyl, X = SH, SnMe₃or AuPPh₃)

Theoretical study of nonlinear optical properties of cobalt bis (dicarbollide) derivatives: the effect of substituents

Hyperpolarizability of 6-vertex carboranes quantum chemical study

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Synthesis of 12-Substituted 1-Carba-closo-dodecaborate Anions and First Hyperpolarizability of the 12-C7H6+-CB11H11- Ylide

Cited by 107 publications

References 34 publications

Sulfur, tin and gold derivatives of 1-(2′-pyridyl)-ortho-carborane, 1-R-2-X-1,2-C2B10H10(R = 2′-pyridyl, X = SH, SnMe3or AuPPh3)

Sulfur, tin and gold derivatives of 1-(2′-pyridyl)-ortho-carborane, 1-R-2-X-1,2-C2B10H10(R = 2′-pyridyl, X = SH, SnMe3or AuPPh3)

Theoretical study of nonlinear optical properties of cobalt bis (dicarbollide) derivatives: the effect of substituents

Hyperpolarizability of 6-vertex carboranes quantum chemical study

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Synthesis of 12-Substituted 1-Carba-closo-dodecaborate Anions and First Hyperpolarizability of the 12-C₇H₆⁺-CB₁₁H₁₁^- Ylide

Sulfur, tin and gold derivatives of 1-(2′-pyridyl)-ortho-carborane, 1-R-2-X-1,2-C₂B₁₀H₁₀(R = 2′-pyridyl, X = SH, SnMe₃or AuPPh₃)

Sulfur, tin and gold derivatives of 1-(2′-pyridyl)-ortho-carborane, 1-R-2-X-1,2-C₂B₁₀H₁₀(R = 2′-pyridyl, X = SH, SnMe₃or AuPPh₃)