Nonlinear optical properties of transition metal acetylides and their derivatives

Powell, Clem E.; Humphrey, Mark G.

doi:10.1016/j.ccr.2004.03.009

Cited by 368 publications

(267 citation statements)

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“…[9,10] In complementary studies in the field of optics, [23] we have recently demonstrated that electrochemical generation of the various redox congeners of the dinuclear Fe(II)/Ru(II) complex 1 (Scheme 1) [24] provides a means to modulate the linear and nonlinear optical properties of a solution of these compounds. Taken together, these developments strongly suggest that hybrid junctions incorporating such carbon-rich molecules offer significant potential for realization of a variety of molecule-based devices.…”

mentioning

confidence: 99%

Silicon Surface‐Bound Redox‐Active Conjugated Wires Derived From Mono‐ and Dinuclear Iron(II) and Ruthenium(II) Oligo(phenyleneethynylene) Complexes

et al. 2008

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Functional molecular materials are playing an everincreasing role in the fabrication of smart integrated devices that can perform inter alia logic operations. [1][2][3][4][5][6] As a result, the nano-engineering of molecular systems on surfaces has recently become a major focus of activity in the design and tailored construction of innovative materials. [7] The modification of conducting surfaces at the molecular level with redoxactive ''building blocks'' constitutes a powerful approach to the fabrication of such materials, particularly when the goal is integrated systems devoted to information storage or transfer. [8][9][10] For such applications, technologically relevant semiconducting surfaces, such as doped silicon, constitute particularly attractive substrates; indeed, silicon surfaces covalently derivatized with reversible redox-center-terminated organic monolayers [1,2,8,[11][12][13][14] have recently been prepared and examined to determine if molecular memories could result from such hybrid junctions. In parallel with these seminal studies, there have been relevant developments with redoxactive carbon-rich group 8 organometallics. These compounds are ideal candidates for reversible charge storage at the molecular level, [15][16][17][18][19][20] and recently Fehlner, Blum, and Rigaut have independently established that both homo-and heteropolynuclear representatives of this class of molecules can be anchored on conducting silicon [9,10] or gold [21,22] interfaces.The studies of bundles/monolayers on gold have revealed far better conduction through these organometallic substrates than through purely organic analogues of similar length, [21,22] while the studies on silicon surfaces have shown that a given redox state of the immobilized molecules can be generated by application of a suitably chosen electrical potential to this hybrid junction. [9,10] In complementary studies in the field of optics, [23] we have recently demonstrated that electrochemical generation of the various redox congeners of the dinuclear Fe(II)/Ru(II) complex 1 (Scheme 1) [24] provides a means to modulate the linear and nonlinear optical properties of a solution of these compounds. Taken together, these developments strongly suggest that hybrid junctions incorporating such carbon-rich molecules offer significant potential for realization of a variety of molecule-based devices. In view of these stimulating prospects, we report herein (i) the successful covalent assembly of electron-rich mononuclear Fe(II) (2 1 -2 3 ) and dinuclear Fe(II)/Ru(II) acetylides (3; Scheme 1) on monocrystalline silicon surfaces following a new and straightforward approach; and (ii) preliminary results defining the facile electron transfer between the semiconducting silicon surface and the immobilized redox-active molecules.To functionalize the silicon surface, we extended the hydrosilylation route developed for purely organic terminal alkynes [25] to organometallic substrates possessing a terminal alkyne moiety. Thus, solutions of the complexes 2 0 -2 3 [26] (...

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Silicon Surface‐Bound Redox‐Active Conjugated Wires Derived From Mono‐ and Dinuclear Iron(II) and Ruthenium(II) Oligo(phenyleneethynylene) Complexes

et al. 2008

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“…In particular, organic molecules are studied frequently because of their larger NLO susceptibilities, with π-electron cloud movement from donor to acceptor, fast NLO response times, high laser damage thresholds and low dielectric constants. In addition to these advantages, the organic molecules also have disadvantages, including generally low thermal stability, facile relaxation to random orientations and in the UV-Vis region, the low energy transitions result in a trade-off between their nonlinear efficiency and optical transparency [54][55][56]. The usage of organic molecules as ligands can overcome the disadvantages.…”

Section: Second-order Nlo Propertiesmentioning

confidence: 99%

Crystal structure, spectral characterization, molecular modeling studies and structural effects of the proton transfer process for (E)-5-methoxy-2-[(3,4-dimethylphenylimino) methyl]phenol

Kırca

Tarı

Kaştaş

et al. 2017

Maced. J. Chem. Chem. Eng.

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The main purpose of this study is to characterize a new organic material, (E)-5-methoxy-2-[(3,4-dimethylphenylimino)methyl]phenol, which was synthesized and grown as a single crystal. The molecular structure and spectroscopic properties of the ortho-hydroxy Schiff base compound were determined by X-ray diffraction analysis, Fourier-transform infrared (FT-IR), ultraviolet-visible (UV-Vis) and nuclear magnetic resonance (NMR) spectroscopy techniques, experimentally and computationally with density functional theory (DFT) calculations. X-ray and UV-Vis studies show that the compound exists in an OH tautomeric form in the solid and solvent media. The gas phase geometry optimizations of two possible forms of the title compound, resulting from the prototropic tautomerism, were obtained using DFT calculations at the B3LYP/6-311G+(d,p) level of theory. A relaxed potential energy surface (PES) scan was performed based on the optimized geometry of the OH tautomeric form by varying the redundant internal coordinate, the O-H bond distance. According to the PES scan process, the molecular geometry is strongly affected by the intramolecular proton transfer. The calculated first hyperpolarizability indicates that the compound could be a good material for non-linear optical applications.Keywords: Schiff base; prototropic tautomerism; intramolecular proton transfer; NLO; DFT КРИСТАЛНА СТРУКТУРА, СПЕКТРАЛНА КАРАКТЕРИЗАЦИЈА, СТУДИИ ЗА МОЛЕКУСКО МОДЕЛИРАЊЕ И СТРУКТУРНИ ЕФЕКТИ ОД ПРОЦЕСОТ НА ПРОТОН ТРАНСФЕР ЗА (E)-5-МЕТОКСИ-2-[(3,4-ДИМЕТИЛФЕНИЛИМИНО)МЕТИЛ]ФЕНОЛГлавна цел на ова истражување е да се карактеризира нов органски материјал, (E)-5-метокси-2-[(3,4-диметилфенилимино)метил]фенол, што беше синтетизиран и израснат како монокристал. Молекулската структура и спекторскопските својства на орто-хидрокси Шифовата база беа определени експериментално со помош на рендгенска дифракциска анализа, Фуриеова трансформна инфрацрвена спектроскопија (FTIR), ултравиолетова спектроскопија (UV-Vis) и нуклеарно-магнетна спектроскопска анализа и пресметковно со помош на теоријата на густината на функционалот (DFT). Испитувањата со рендгенската дифракција и UV-Vis покажуваат дека соединението постои во OH тавтомерна форма во цврста состојба и во раствор. Геометриската оптимизација во гасна фаза на двете можни форми на наведеното соединение кои се резултат на прототропен тавтомеризам беа добиени со пресметки според DFT на нивото на теоријата B3LYP/6-311G+(d,p). Скенирањето на површината на релаксираната потенцијална енергија (PES) беше изведено врз оптимизираната геометрија на ОН тавтомерната форма со менување на редундантната внатрешна координата, должината на О-Н врската. Според скенот на процесот на РЕЅ, молекулската геометрија е под силно влијание на интрамолекулскиот B. K. Kırca, G. Ö. Tarı, Ç. A. Kaştaş, M. Odabaşoğlu, O. Büyükgüngö Maced. J. Chem. Chem. Eng. 36 (1), xx-xx (2017) 266 трансфер на протони. Пресметаната прва хиперполаризабилност укажува дека соединението би било добар материјал за нелинеарни оптички апликации.Клучни зборови: Шиф...

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“…For this reason, we became aware of the ligand trimethysilylethynyltetramethylcyclopentadiene CpMe 4 (C≡CSiMe 3 )H. CpMe 4 (C≡CSiMe 3 ) − has been used before in group 8 chemistry. The postmodification of η 5 -CpMe 4 (C≡CSiMe 3 ) − metal complexes may include access to metal acetylides [13,14], metal alkyne complexes [15,16], Sonogashira couplings [17][18][19], click reactions [20,21] and cyclizations [22][23][24]. : Na1-C6 2.691(4), Na1-C7 2.673(4), Na1-C8 2.672(4), Na1-C9 2.717(4), Na1-C10 2.736(4), C4-C5 1.223(6), Na1-O1 2.289(3), Na1-O2 2.321(3), Na1-O3 2.293(3), O1-Na1-O2 96.70(2), O2-Na1-O3 95.75 (12), O3-Na1-O1 96.14 (12).…”

Section: Introductionmentioning

confidence: 99%

Alkali and Alkaline Earth Metal Complexes Ligated by an Ethynyl Substituted Cyclopentadienyl Ligand

Seifert

Roesky

2017

Inorganics

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Nonlinear optical properties of transition metal acetylides and their derivatives

Cited by 368 publications

References 78 publications

Silicon Surface‐Bound Redox‐Active Conjugated Wires Derived From Mono‐ and Dinuclear Iron(II) and Ruthenium(II) Oligo(phenyleneethynylene) Complexes

Silicon Surface‐Bound Redox‐Active Conjugated Wires Derived From Mono‐ and Dinuclear Iron(II) and Ruthenium(II) Oligo(phenyleneethynylene) Complexes

Crystal structure, spectral characterization, molecular modeling studies and structural effects of the proton transfer process for (E)-5-methoxy-2-[(3,4-dimethylphenylimino) methyl]phenol

Alkali and Alkaline Earth Metal Complexes Ligated by an Ethynyl Substituted Cyclopentadienyl Ligand

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