Second-order nonlinear optical materials: recent advances in chromophore design

Verbiest, Thierry; Houbrechts, Stephan; Kauranen, Martti; Clays, Koen; Persoons, André

doi:10.1039/a703434b

Cited by 593 publications

(306 citation statements)

References 91 publications

Supporting

Mentioning

300

Contrasting

Order By: Relevance

“…Calculation of the static quadratic hyperpolarizability, o , gives values ranging from 46 to 211 (10 -30 esu), which are of the same order of magnitude or higher than those of organic 4,4′-disubstituted stilbenes, like trans-4-dimethylamino-4′-nitrostilbene (DANS, included in Table 8), 51 and other organic NLO compounds. 52 These enhanced NLO properties can be the result of the polarization along the C-Pt bond of the NCN-PtCl moiety. 53,54 The values are also in line with and sometimes higher than other organometallic molecules 52 including the stilbenoid and stilbazole ferrocene analogues.…”

mentioning

confidence: 99%

“…52 These enhanced NLO properties can be the result of the polarization along the C-Pt bond of the NCN-PtCl moiety. 53,54 The values are also in line with and sometimes higher than other organometallic molecules 52 including the stilbenoid and stilbazole ferrocene analogues. 2,46,55 An example of a p-NO 2 -substituted stilbenoid ferrocene analogue, [Fe(C 5 H 5 )(C 5 H 4 -C 2 H 2 -p-C 6 H 4 NO 2 )], 3 is included in Table 8.…”

mentioning

confidence: 99%

See 1 more Smart Citation

Substituted 4,4′-Stilbenoid NCN-Pincer Platinum(II) Complexes. Luminescence and Tuning of the Electronic and NLO Properties and the Application in an OLED

et al. 2008

Self Cite

View full text Add to dashboard Cite

A series of 4,4′-disubstituted organic-organometallic stilbenes, i.e., the 4′-substituted stilbenoid-NCN-pincer platinum(II) complexes [PtCl(NCN-R-4)] (NCN-R-4 ) [C 6 H 2 (CH 2 NMe 2 ) 2 -2,6-R-4] -in which R ) C 2 H 2 C 6 H 4 -R′-4′ with R′ ) NPh 2 , NMe 2 , OMe, SiMe 3 H, I, CN, NO 2 ) (1-8), were studied for their electronic, electrochemical, and NLO properties. Complex 7 was also chemically oxidized using Cu(II)Cl 2 , yielding the [Pt(IV)Cl 3 (NCN(C 2 H 2 C 6 H 4 -CN-4′)-4)] complex 11. In contrast to 1 and 7, 11 did not show luminescent properties in solution at room temperature. In the solid state (X-ray crystallography) 11 has an overall bent structure, with the pincer moiety and the cyano group beneath the plane of the central double bond. Stilbenoid pincer complex 1 (R′ ) NPh 2 ) was also studied with UV/vis spectroscopy in a series of different solvents. The compound shows an intense low-energy transition band, appearing at a lower energy (λ max ) 374-379 nm) than 2 (R′ ) NMe 2 ), which contains a stronger donor group. The UV/vis absorption data of a selected series of stilbenoid pincer platinum complexes were interpreted in terms of a qualitative orbital model based on DFT and TD-DFT calculations. The trends observed in the transition energies correlate well with the donor/acceptor properties of the substituents. It was shown that the HOMO-LUMO gap of the stilbenoid pincer platinum compounds decreases when going from an electron-neutral group (R′ ) H) toward an electron-donating (R′ ) NMe 2 ) or -accepting (R′ ) NO 2 ) group. The fluorescence properties of 1 were also investigated using fluorescence and laser spectroscopy, showing that the metal center favors nonradiative decay from the excited state to the ground state. For 7 (R′ ) CN), solid-state 13 C CP/MAS NMR measurements were performed, and a value of 1 J( 13 C, 195 Pt) ) 1003 ( 15 Hz was obtained for the C ipso carbon, reflecting π-contributions in the carbon-metal bond. The cyclic voltammetry study on the complexes revealed an irreversible oxidation from Pt(II) to Pt(IV). In general the oxidation potential is influenced by the electronic character of the R′ substituent. The influence of the para R′ substituent on the hyperpolarizability of the compound was investigated using the femtosecond (frequencyresolved) HRS technique. For 1-7 good zzz values were measured ( zzz ranging from (164-1324) × 10 -30 esu) with the highest value for 6 (R′ ) I). The higher zzz values were found for the compounds that contain a low-energy UV/vis absorption band and/or a large absorption coefficient. Donor-acceptor complexes 7 and 8 were successfully applied in an organic light-emitting diode (OLED). In the electroluminescence spectrum of 7 (R′ ) CN) a low-energy emission band was observed at 643 nm. This band also appeared in the solid-state luminescence spectra of 7, however, only at low temperatures (298-15 K). The emission band was assigned to result from a triplet excited state. The present study shows that the introduction of a NCN-pincer platinum fragment ...

show abstract

mentioning

confidence: 99%

mentioning

confidence: 99%

Substituted 4,4′-Stilbenoid NCN-Pincer Platinum(II) Complexes. Luminescence and Tuning of the Electronic and NLO Properties and the Application in an OLED

et al. 2008

Self Cite

View full text Add to dashboard Cite

show abstract

“…Generally, an increase in the β value is accompanied by a bathochromic shift due to a larger π-conjugated length and/or stronger donor and acceptor ability [9][10][11][12][13]. Therefore, there is always a tradeoff between nonlinearity and transparency [14][15][16][17][18][19][20][21][22][23]. To resolve this problem, we had designed and synthesized a series of H-typed chromophores with two parallel and nonconjugated D-π-A units [24][25][26][27].…”

Section: Introductionmentioning

confidence: 99%

Theoretical Study of Effect of the Number of N,N-dimethyl-4-nitroaniline Units in Novel “Parallel Connection” Chromophores on Its Nonlinear Optical Properties

Zhang

Cao

Zhaobing

2012

ISRN Physical Chemistry

View full text Add to dashboard Cite

Design of "parallel connection" chromophores could give a way of acquiring effective chromophores. The semiempirical method ZINDO was employed to study relationship between static first hyperpolarizabilities of "parallel connection" chromophores and the number of parallel nonconjugated N,N-dimethyl-4-nitroaniline (DMNA) units in the chromophore. The results show that the chromophore containing three parallel non-conjugated DMNA units exhibits the highest static first hyperpolarizability, which is 1.8 times that of chromophore DMNA. However, static first hyperpolarizabilities of the chromophores containing four or five DMNA units are very small. The absorption maximum wavelength (λ max ) of "parallel connection" chromophores is remarkably shorter (34.9 nm-38.1 nm) than that of 1DMNA. Therefore, the "parallel connection" chromophore containing three DMNA units would be an effective chromophore with a large first hyperpolarizability and a good optical transparency. It could give a useful suggestion for designing effective chromophores containing parallel non-conjugated D-π-A units.

show abstract

“…Hyperpolarizability is usually associated with an extended º -conjugated system, capped with donor and acceptor substituents. The e±ciency of the º -bridge as a pathway for charge transfer between donor and acceptor groups has been the subject of extensive theoretical and experimen-tal studies [4], [5], [6], [7], [8], [9]. A variety of º -conjugated moieties, namely polyene and polyyne chains, aromatic cycles such as benzene, pyridine, thiophene and other heterocycles, as well as their combinations, have been investigated.…”

Section: Introductionmentioning

confidence: 99%

Hyperpolarizability of 6-vertex carboranes quantum chemical study

Suponitsky

Timofeeva

2003

Open Chemistry

View full text Add to dashboard Cite

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.

show abstract

Second-order nonlinear optical materials: recent advances in chromophore design

Cited by 593 publications

References 91 publications

Substituted 4,4′-Stilbenoid NCN-Pincer Platinum(II) Complexes. Luminescence and Tuning of the Electronic and NLO Properties and the Application in an OLED

Substituted 4,4′-Stilbenoid NCN-Pincer Platinum(II) Complexes. Luminescence and Tuning of the Electronic and NLO Properties and the Application in an OLED

Theoretical Study of Effect of the Number of N,N-dimethyl-4-nitroaniline Units in Novel “Parallel Connection” Chromophores on Its Nonlinear Optical Properties

Hyperpolarizability of 6-vertex carboranes quantum chemical study

Contact Info

Product

Resources

About