Organometallic complexes for nonlinear optics. 3.1 Molecular quadratic hyperpolarizabilities of ene-, imine-, and azo-linked ruthenium σ-acetylides: X-ray crystal structure of Ru((E)-4,4′-C≡CC6H4CH=CHC6H 4NO2)(PPh3)2(η-C 5H5)

Ian R. Whittall; Mark G. Humphrey; André Persoons; Stephan Houbrechts

doi:10.1021/om950487y

Organometallic complexes for nonlinear optics. 3.¹ Molecular quadratic hyperpolarizabilities of ene-, imine-, and azo-linked ruthenium σ-acetylides: X-ray crystal structure of Ru((E)-4,4′-C≡CC₆H₄CH=CHC₆H ₄NO₂)(PPh₃)₂(η-C ₅H₅)

Ian R. Whittall, Mark G. Humphrey^*, André Persoons, Stephan Houbrechts

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

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Abstract

The series of complexes Ru((E)-4,4′-C≡CC₆H₄X=CHC₆H ₄NO₂)(PR₃)₂(η-C ₅H₅) (X = CH, R = Ph 11a; X = CH, R = Me, 11b; X = N, R = Ph, 12a; X = N, R = Me, 12b) has been synthesized by reaction of RuCl(PR₃)₂(η-C₅H₅) with (E)-4,4′-HC≡CC₆H₄X=CHC₆H ₄NO₂ and deprotonation of the intermediate vinylidene complex. Complex 11a has been structurally characterized; it is the first example of a donor-acceptor organometallic "extended" chromophore bearing the prototypical acceptor -NO₂ to be crystallographically studied. Molecular quadratic hyperpolarizabilities at 1.9 μm were evaluated computationally for the complexes above and imine- and azo-linked analogues by employing ZINDO with crystallographically obtained atomic coordinates. The results are consistent with a substantial increase in quadratic nonlinearity for (i) chain lengthening of the organometallic chromophore (replacing 4-C≡CC₆H₄NO₂ by (E)-4,4′-C≡CC₆H₄CH=CHC₆H ₄NO₂) and (ii) an azo linkage compared with an ene linkage (replacing (E)-4,4′-C≡CC₆H₄CH=CHC₆H ₄NO₂ by (E)-4,4′-C≡CC₆H₄N=NC₆H ₄NO₂). Little variation in computed response was found upon substituting an imine linkage for an ene linkage in the organometallic chromophore (replacing (E)-4,4′-C≡CC₆H₄CH=CHC₆H ₄NO₂ by (E)-4,4′-C≡CC₆H₄N=CHC₆H ₄NO₂ or (E)-4,4′-C≡CC₆H₄-CH≡NC₆H ₄NO₂). Molecular quadratic optical nonlinearities were determined experimentally for 11a, 12a, and Ru(C≡CC₆H₄NO₂-4)(PR₃) ₂(η-C₅H₅) (R = Ph, Me) by electric-field-induced second-harmonic generation (EFISH; 11a and 12a only) and hyper-Rayleigh scattering (HRS) techniques. EFISH-derived μβ₁₀₆₄ values for 11a (9700 × 10-⁴⁸ cm⁵ esu^-1) and 12a (5800 × 10^-48 cm⁵ esu^-1) are large compared to those for other organometallic complexes. Resonance-enhanced quadratic nonlinearities at 1.06 μm from HRS are large (1455 × 10^-30 cm⁵ esu^-1, 11a; 840 × 10^-30 cm⁵ esu^-1, 12a). Two-level-corrected values confirm a substantial increase in quadratic nonlinearity for chain lengthening but suggest a significant decrease in nonlinearity on replacing an ene linkage by an imine linkage; the latter is contrary to the ZINDO result, and the reasons for this are discussed.

Original language	English
Pages (from-to)	1935-1941
Number of pages	7
Journal	Organometallics
Volume	15
Issue number	7
DOIs	https://doi.org/10.1021/om950487y
Publication status	Published - 2 Apr 1996

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Whittall, I. R., Humphrey, M. G., Persoons, A., & Houbrechts, S. (1996). Organometallic complexes for nonlinear optics. 3.¹ Molecular quadratic hyperpolarizabilities of ene-, imine-, and azo-linked ruthenium σ-acetylides: X-ray crystal structure of Ru((E)-4,4′-C≡CC₆H₄CH=CHC₆H ₄NO₂)(PPh₃)₂(η-C ₅H₅). Organometallics, 15(7), 1935-1941. https://doi.org/10.1021/om950487y

@article{aed10917d89b44078c2536309020e955,

title = "Organometallic complexes for nonlinear optics. 3.1 Molecular quadratic hyperpolarizabilities of ene-, imine-, and azo-linked ruthenium σ-acetylides: X-ray crystal structure of Ru((E)-4,4′-C≡CC6H4CH=CHC6H 4NO2)(PPh3)2(η-C 5H5)",

abstract = "The series of complexes Ru((E)-4,4′-C≡CC6H4X=CHC6H 4NO2)(PR3)2(η-C 5H5) (X = CH, R = Ph 11a; X = CH, R = Me, 11b; X = N, R = Ph, 12a; X = N, R = Me, 12b) has been synthesized by reaction of RuCl(PR3)2(η-C5H5) with (E)-4,4′-HC≡CC6H4X=CHC6H 4NO2 and deprotonation of the intermediate vinylidene complex. Complex 11a has been structurally characterized; it is the first example of a donor-acceptor organometallic {"}extended{"} chromophore bearing the prototypical acceptor -NO2 to be crystallographically studied. Molecular quadratic hyperpolarizabilities at 1.9 μm were evaluated computationally for the complexes above and imine- and azo-linked analogues by employing ZINDO with crystallographically obtained atomic coordinates. The results are consistent with a substantial increase in quadratic nonlinearity for (i) chain lengthening of the organometallic chromophore (replacing 4-C≡CC6H4NO2 by (E)-4,4′-C≡CC6H4CH=CHC6H 4NO2) and (ii) an azo linkage compared with an ene linkage (replacing (E)-4,4′-C≡CC6H4CH=CHC6H 4NO2 by (E)-4,4′-C≡CC6H4N=NC6H 4NO2). Little variation in computed response was found upon substituting an imine linkage for an ene linkage in the organometallic chromophore (replacing (E)-4,4′-C≡CC6H4CH=CHC6H 4NO2 by (E)-4,4′-C≡CC6H4N=CHC6H 4NO2 or (E)-4,4′-C≡CC6H4-CH≡NC6H 4NO2). Molecular quadratic optical nonlinearities were determined experimentally for 11a, 12a, and Ru(C≡CC6H4NO2-4)(PR3) 2(η-C5H5) (R = Ph, Me) by electric-field-induced second-harmonic generation (EFISH; 11a and 12a only) and hyper-Rayleigh scattering (HRS) techniques. EFISH-derived μβ1064 values for 11a (9700 × 10-48 cm5 esu-1) and 12a (5800 × 10-48 cm5 esu-1) are large compared to those for other organometallic complexes. Resonance-enhanced quadratic nonlinearities at 1.06 μm from HRS are large (1455 × 10-30 cm5 esu-1, 11a; 840 × 10-30 cm5 esu-1, 12a). Two-level-corrected values confirm a substantial increase in quadratic nonlinearity for chain lengthening but suggest a significant decrease in nonlinearity on replacing an ene linkage by an imine linkage; the latter is contrary to the ZINDO result, and the reasons for this are discussed.",

author = "Whittall, \{Ian R.\} and Humphrey, \{Mark G.\} and Andr{\'e} Persoons and Stephan Houbrechts",

year = "1996",

month = apr,

day = "2",

doi = "10.1021/om950487y",

language = "English",

volume = "15",

pages = "1935--1941",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "7",

}

Whittall, IR, Humphrey, MG, Persoons, A & Houbrechts, S 1996, 'Organometallic complexes for nonlinear optics. 3.¹ Molecular quadratic hyperpolarizabilities of ene-, imine-, and azo-linked ruthenium σ-acetylides: X-ray crystal structure of Ru((E)-4,4′-C≡CC₆H₄CH=CHC₆H ₄NO₂)(PPh₃)₂(η-C ₅H₅)', Organometallics, vol. 15, no. 7, pp. 1935-1941. https://doi.org/10.1021/om950487y

Organometallic complexes for nonlinear optics. 3.¹ Molecular quadratic hyperpolarizabilities of ene-, imine-, and azo-linked ruthenium σ-acetylides: X-ray crystal structure of Ru((E)-4,4′-C≡CC₆H₄CH=CHC₆H ₄NO₂)(PPh₃)₂(η-C ₅H₅). / Whittall, Ian R.; Humphrey, Mark G.; Persoons, André et al.
In: Organometallics, Vol. 15, No. 7, 02.04.1996, p. 1935-1941.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Organometallic complexes for nonlinear optics. 3.1 Molecular quadratic hyperpolarizabilities of ene-, imine-, and azo-linked ruthenium σ-acetylides

T2 - X-ray crystal structure of Ru((E)-4,4′-C≡CC6H4CH=CHC6H 4NO2)(PPh3)2(η-C 5H5)

AU - Whittall, Ian R.

AU - Humphrey, Mark G.

AU - Persoons, André

AU - Houbrechts, Stephan

PY - 1996/4/2

Y1 - 1996/4/2

N2 - The series of complexes Ru((E)-4,4′-C≡CC6H4X=CHC6H 4NO2)(PR3)2(η-C 5H5) (X = CH, R = Ph 11a; X = CH, R = Me, 11b; X = N, R = Ph, 12a; X = N, R = Me, 12b) has been synthesized by reaction of RuCl(PR3)2(η-C5H5) with (E)-4,4′-HC≡CC6H4X=CHC6H 4NO2 and deprotonation of the intermediate vinylidene complex. Complex 11a has been structurally characterized; it is the first example of a donor-acceptor organometallic "extended" chromophore bearing the prototypical acceptor -NO2 to be crystallographically studied. Molecular quadratic hyperpolarizabilities at 1.9 μm were evaluated computationally for the complexes above and imine- and azo-linked analogues by employing ZINDO with crystallographically obtained atomic coordinates. The results are consistent with a substantial increase in quadratic nonlinearity for (i) chain lengthening of the organometallic chromophore (replacing 4-C≡CC6H4NO2 by (E)-4,4′-C≡CC6H4CH=CHC6H 4NO2) and (ii) an azo linkage compared with an ene linkage (replacing (E)-4,4′-C≡CC6H4CH=CHC6H 4NO2 by (E)-4,4′-C≡CC6H4N=NC6H 4NO2). Little variation in computed response was found upon substituting an imine linkage for an ene linkage in the organometallic chromophore (replacing (E)-4,4′-C≡CC6H4CH=CHC6H 4NO2 by (E)-4,4′-C≡CC6H4N=CHC6H 4NO2 or (E)-4,4′-C≡CC6H4-CH≡NC6H 4NO2). Molecular quadratic optical nonlinearities were determined experimentally for 11a, 12a, and Ru(C≡CC6H4NO2-4)(PR3) 2(η-C5H5) (R = Ph, Me) by electric-field-induced second-harmonic generation (EFISH; 11a and 12a only) and hyper-Rayleigh scattering (HRS) techniques. EFISH-derived μβ1064 values for 11a (9700 × 10-48 cm5 esu-1) and 12a (5800 × 10-48 cm5 esu-1) are large compared to those for other organometallic complexes. Resonance-enhanced quadratic nonlinearities at 1.06 μm from HRS are large (1455 × 10-30 cm5 esu-1, 11a; 840 × 10-30 cm5 esu-1, 12a). Two-level-corrected values confirm a substantial increase in quadratic nonlinearity for chain lengthening but suggest a significant decrease in nonlinearity on replacing an ene linkage by an imine linkage; the latter is contrary to the ZINDO result, and the reasons for this are discussed.

AB - The series of complexes Ru((E)-4,4′-C≡CC6H4X=CHC6H 4NO2)(PR3)2(η-C 5H5) (X = CH, R = Ph 11a; X = CH, R = Me, 11b; X = N, R = Ph, 12a; X = N, R = Me, 12b) has been synthesized by reaction of RuCl(PR3)2(η-C5H5) with (E)-4,4′-HC≡CC6H4X=CHC6H 4NO2 and deprotonation of the intermediate vinylidene complex. Complex 11a has been structurally characterized; it is the first example of a donor-acceptor organometallic "extended" chromophore bearing the prototypical acceptor -NO2 to be crystallographically studied. Molecular quadratic hyperpolarizabilities at 1.9 μm were evaluated computationally for the complexes above and imine- and azo-linked analogues by employing ZINDO with crystallographically obtained atomic coordinates. The results are consistent with a substantial increase in quadratic nonlinearity for (i) chain lengthening of the organometallic chromophore (replacing 4-C≡CC6H4NO2 by (E)-4,4′-C≡CC6H4CH=CHC6H 4NO2) and (ii) an azo linkage compared with an ene linkage (replacing (E)-4,4′-C≡CC6H4CH=CHC6H 4NO2 by (E)-4,4′-C≡CC6H4N=NC6H 4NO2). Little variation in computed response was found upon substituting an imine linkage for an ene linkage in the organometallic chromophore (replacing (E)-4,4′-C≡CC6H4CH=CHC6H 4NO2 by (E)-4,4′-C≡CC6H4N=CHC6H 4NO2 or (E)-4,4′-C≡CC6H4-CH≡NC6H 4NO2). Molecular quadratic optical nonlinearities were determined experimentally for 11a, 12a, and Ru(C≡CC6H4NO2-4)(PR3) 2(η-C5H5) (R = Ph, Me) by electric-field-induced second-harmonic generation (EFISH; 11a and 12a only) and hyper-Rayleigh scattering (HRS) techniques. EFISH-derived μβ1064 values for 11a (9700 × 10-48 cm5 esu-1) and 12a (5800 × 10-48 cm5 esu-1) are large compared to those for other organometallic complexes. Resonance-enhanced quadratic nonlinearities at 1.06 μm from HRS are large (1455 × 10-30 cm5 esu-1, 11a; 840 × 10-30 cm5 esu-1, 12a). Two-level-corrected values confirm a substantial increase in quadratic nonlinearity for chain lengthening but suggest a significant decrease in nonlinearity on replacing an ene linkage by an imine linkage; the latter is contrary to the ZINDO result, and the reasons for this are discussed.

UR - https://www.scopus.com/pages/publications/0037820823

U2 - 10.1021/om950487y

DO - 10.1021/om950487y

M3 - Article

AN - SCOPUS:0037820823

SN - 0276-7333

VL - 15

SP - 1935

EP - 1941

JO - Organometallics

JF - Organometallics

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