Theoretical investigation of second-order nonlinear optical response — Hexamolybdate as a superior donor over metal carbonyl complexes in the D–π–A model

Density functional theory (DFT) calculations were carried out to investigate the nonlinear optical (NLO) response for the donor-conjugated bridge-accepter (D–π–A) model of p-nitroaniline (PNA) – hexamolybdate derivatives and PNA–metal–carbonyl complexes. The bond length alternation (BLA) values decrease with lengthening of the π-conjugated bridge, especially for PNA–hexamolybdate derivatives, which dramatically enhances the NLO response. In addition, the introduction of Mo≡N in PNA–hexamolybdate derivatives is expected to provide a better electron transition channel, consequently generating lower BLA values and an outstanding NLO response compared with PNA–metal–carbonyl complexes. It is shown that the hexamolybdate acts as an electron donor when incorporating metal–carbonyl complexes into one molecule. All these behaviors reflect the superiority of hexamolybdate as a donor moiety in the D–π–A model for the design of potential NLO materials.

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Intra- and intermolecular interactions in a series of chlorido-tricarbonyl-diazabutadienerhenium(I) complexes: structural and theoretical studies

Acta Crystallographica Section B Structural Science Crystal Engineering and Materials ◽

10.1107/s2052520620004333 ◽

2020 ◽

Vol 76 (3) ◽

pp. 417-426 ◽

Cited By ~ 2

Author(s):

Reza Kia ◽

Azadeh Kalaghchi

Keyword(s):

Intermolecular Interactions ◽

Density Functional ◽

Metal Carbonyl ◽

Lone Pair ◽

Carbonyl Complexes ◽

X Ray Diffraction ◽

Functional Theory ◽

X Ray ◽

Covalent Interaction ◽

Metal Carbonyl Complexes

A series of new chlorido-tricarbonylrhenium(I) complexes bearing alkyl-substituted diazabutadiene (DAB) ligands, namely N,N′-bis(2,4-dimethylbenzene)-1,4-diazabutadiene (L1), N,N′-bis(2,4-dimethylbenzene)-2,3-dimethyl-1,4-diazabutadiene (L2), N,N′-bis(2,4,6-trimethylbenzene)-2,3-dimethyl-1,4-diazabutadiene (L3) and N,N′-bis(2,6-diisopropylbenzene)-1,4-diazabutadiene (L4), were synthesized and investigated. The crystal structures have been fully characterized by X-ray diffraction and spectroscopic methods. Density functional theory, natural bond orbital and non-covalent interaction index methods have been used to study the optimized geometry in the gas phase and intra- and intermolecular interactions in the complexes, respectively. The most important studied interactions in these metal carbonyl complexes are n→π*, n→σ* and π→π*. Among complexes 1–4, only 2 shows interesting intermolecular n→π* interactions due to lp(C[triple-bond]O)...π* and lp(Cl)...π* (lp = lone pair) contacts.

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Metal carbonyl complexes of potentially ambidentate 2,1,3-benzothiadiazole and 2,1,3-benzoselenadiazole acceptors

Zeitschrift für Naturforschung B ◽

10.1515/znb-2017-0100 ◽

2017 ◽

Vol 72 (11) ◽

pp. 839-846

Author(s):

Sebastian Plebst ◽

Martina Bubrin ◽

David Schweinfurth ◽

Stanislav Záliš ◽

Wolfgang Kaim

Keyword(s):

Crystal Structure ◽

Density Functional Theory ◽

Electron Transfer ◽

Density Functional ◽

Metal Carbonyl ◽

Density Functional Theory Calculations ◽

Carbonyl Complexes ◽

Functional Theory ◽

Metal Carbonyl Complexes ◽

Reduced Forms

AbstractThe compounds [W(CO)5(btd)], [W(CO)5(bsd] and [Re(CO)3(bpy)(bsd)](BF4), btd=2,1,3-benzothiadiazole and bsd=2,1,3-benzoselenadiazole were isolated and characterized experimentally (crystal structure, spectroscopy, spectroelectrochemistry) and by density functional theory calculations. The results confirm single N-coordination in all cases, binding to Se was calculated to be less favorable. Studies of one-electron reduced forms indicate that the N-coordination is maintained during electron transfer.

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Symmetry Force Fields for Neutral and Ionic Transition Metal Carbonyl Complexes from Density Functional Theory

The Journal of Physical Chemistry A ◽

10.1021/jp983600h ◽

1999 ◽

Vol 103 (10) ◽

pp. 1381-1393 ◽

Cited By ~ 13

Author(s):

Volker Jonas ◽

Walter Thiel

Keyword(s):

Density Functional Theory ◽

Transition Metal ◽

Density Functional ◽

Force Fields ◽

Metal Carbonyl ◽

Carbonyl Complexes ◽

Functional Theory ◽

Metal Carbonyl Complexes ◽

Ionic Transition

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Electronic structure and molecular properties of binuclear group VII pentalene metal carbonyl complexes [C8H6{M(CO3)}2] (M=Mn, Tc, Re, Bh): A relativistic density functional theory study

Polyhedron ◽

10.1016/j.poly.2009.03.016 ◽

2009 ◽

Vol 28 (8) ◽

pp. 1561-1567 ◽

Cited By ~ 8

Author(s):

A. Muñoz-Castro ◽

D. Mac-Leod Carey ◽

R. Arratia-Pérez

Keyword(s):

Density Functional Theory ◽

Electronic Structure ◽

Density Functional ◽

Metal Carbonyl ◽

Molecular Properties ◽

Carbonyl Complexes ◽

Density Functional Theory Study ◽

Functional Theory ◽

Metal Carbonyl Complexes

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Computational Characterization of Bidentate P-Donor Ligands: Direct Comparison to Tolman’s Electronic Parameters

Molecules ◽

10.3390/molecules23123176 ◽

2018 ◽

Vol 23 (12) ◽

pp. 3176 ◽

Cited By ~ 4

Author(s):

Tímea Kégl ◽

Noémi Pálinkás ◽

László Kollár ◽

Tamás Kégl

Keyword(s):

Density Functional Theory ◽

Density Functional ◽

Metal Carbonyl ◽

Donor Ligands ◽

Carbonyl Complexes ◽

Electronic Effects ◽

Functional Theory ◽

Metal Carbonyl Complexes ◽

Electronic Parameters

The applicability of two types of transition-metal carbonyl complexes as appropriate candidates for computationally derived Tolman’s ligand electronic parameters were examined with density functional theory (DFT) calculations employing the B97D3 functional. Both Pd(0)L2(CO) and HRh(I)L2(CO) complexes correlated well with the experimental Tolman Electronic Parameter scale. For direct comparison of the electronic effects of diphosphines with those of monophosphines, the palladium-containing system is recommended. The t r a n s influence of various phosphines did not show a major difference, but the decrease of the H-Rh-P angle from linear can cause a significant change.

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Theoretical exploration to the cation effect on the second-order nonlinear optical properties of Strandberg-type polyoxometalates

Journal of Theoretical and Computational Chemistry ◽

10.1142/s0219633615500078 ◽

2015 ◽

Vol 14 (01) ◽

pp. 1550007 ◽

Cited By ~ 1

Author(s):

Ting Zhang ◽

Wei Guan ◽

Shizheng Wen ◽

Tengying Ma ◽

Likai Yan ◽

...

Keyword(s):

Density Functional ◽

Nonlinear Optical ◽

Dft Method ◽

Transition Metal Ions ◽

Second Order ◽

Functional Theory ◽

Cation Effect ◽

Nlo Response ◽

Polar Materials ◽

Nlo Materials

The combination of cations with octahedral coordinated d0 transition metal ions has been proved to be an effective way for designing new polar materials. So we investigate the second-order nonlinear optical (NLO) properties of Strandberg-type polyoxometalates (POMs) with alkali metal cations M 6 Mo 5 X 2 O 23 ( M = K +, Rb +, Cs +; X = P , As ) and M 4 M o5 X 2 O 21 ( M = K +, Rb +, Cs +; X = S , Se , Te ) by density functional theory (DFT) method. The calculated results show that this kind of Strandberg-type POMs possesses remarkably large molecular second-order NLO polarizability, especially for the Cs 6 Mo 5 P 2 O 23 (system Ic), which has a computed β0 value of 12526 a.u. and might be an excellent second-order NLO material. Moreover, the cations have important impact on the second-order NLO polarizabilities. Therefore, a careful choice of appropriate cations may allow the control of the second-order NLO response on these Strandberg-type POMs, which may provide a new route to design efficient NLO materials.

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Density Functional Theory Predictions of the Nonlinear Optical (NLO) Properties in Triphenylamine based α-Cyanocinnamic Acid Compounds: Effect of Fluorine on NLO Response

Journal of the Mexican Chemical Society ◽

10.29356/jmcs.v62i3.551 ◽

2019 ◽

Vol 62 (3) ◽

Author(s):

Muhammad Ramzan Saeed Ashraf Janjua Janjua

Keyword(s):

Phenyl Ring ◽

Density Functional ◽

Nonlinear Optical ◽

Second Order ◽

Functional Theory ◽

Nlo Properties ◽

Nlo Response ◽

Nlo Materials ◽

Cyanocinnamic Acid ◽

Insight Into

In this study, the energy gaps, second-order nonlinear optical (NLO) properties and dipole polarizabilities of triphenylamine based α-cyanocinnamic acid acetylene derivatives have been investigated via using time-dependent density functional response theory. These compounds were designed theoretically by fluorine (F) atom substitution at different positions of phenyl ring end of the α-cyanocinnamic acid segment. The results have indicated that the systems substituted by fluorine show remarkable NLO second-order response, especially D4 system with computed static second-order polarizability (βtot) of 70537.95 (a.u). Hence, these materials have the likelihood to be an excellent second-order nonlinear optical (NLO) materials. The βtot value suggests that along the x-axis the charge transfer (CT) from triphenylamine to α-cyanocinnamic acid (D-A) plays a key role in NLO response; whereas α-cyanocinnamic acid acts as an acceptor (A) and triphenylamine acts as a donor (D) in all the studied systems. Incorporation of an electron acceptor (F) at the phenyl ring end of the α-cyanocinnamic acid segment increases the computed βtot values. The present investigation therefore provides an important insight into the remarkably greater NLO properties of α-cyanocinnamic acid and triphenylamine attached via acetylene.

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Photoactivatable metal complexes: from theory to applications in biotechnology and medicine

Philosophical Transactions of The Royal Society A Mathematical Physical and Engineering Sciences ◽

10.1098/rsta.2012.0519 ◽

2013 ◽

Vol 371 (1995) ◽

pp. 20120519 ◽

Cited By ~ 111

Author(s):

Nichola A. Smith ◽

Peter J. Sadler

Keyword(s):

Metal Complexes ◽

Density Functional ◽

Metal Carbonyl ◽

Short Review ◽

Photochemical Reactions ◽

Carbonyl Complexes ◽

Functional Theory ◽

Metal Carbonyl Complexes ◽

Recent Developments ◽

Novel Strategy

This short review highlights some of the exciting new experimental and theoretical developments in the field of photoactivatable metal complexes and their applications in biotechnology and medicine. The examples chosen are based on some of the presentations at the Royal Society Discussion Meeting in June 2012, many of which are featured in more detail in other articles in this issue. This is a young field. Even the photochemistry of well-known systems such as metal–carbonyl complexes is still being elucidated. Striking are the recent developments in theory and computation (e.g. time-dependent density functional theory) and in ultrafast-pulsed radiation techniques which allow photochemical reactions to be followed and their mechanisms to be revealed on picosecond/nanosecond time scales. Not only do some metal complexes (e.g. those of Ru and Ir) possess favourable emission properties which allow functional imaging of cells and tissues (e.g. DNA interactions), but metal complexes can also provide spatially controlled photorelease of bioactive small molecules (e.g. CO and NO)—a novel strategy for site-directed therapy. This extends to cancer therapy, where metal-based precursors offer the prospect of generating excited-state drugs with new mechanisms of action that complement and augment those of current organic photosensitizers.

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