Aggregation induced convertible third-order nonlinear optical absorptions of the phenoxazinium containing films prepared by sol–gel method

Zhang, Fei; Miao, Jia-Tao; Fang, Yu; Sun, Rong; Guo, Xiaozhi; Song, Yinglin; Ge, Jian‐Feng

doi:10.1016/j.dyepig.2014.09.022

Cited by 6 publications

(5 citation statements)

References 35 publications

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“…That the adsorption pattern of 7 is different from those for 2−6 is likely due to its unique structure. 85 Nevertheless, for all of 2− 7, the valley-to-peak configuration of the curves of refractive data, evaluated by dividing the normalized Z-scan data obtained under closed aperture by the normalized Z-scan data collected under the open-aperture configuration (Figure 8 for 2 and 7 and Figure S7 for 3−6), suggests that the nonlinear refractive index change is positive and thus an indication of a strong selffocusing effect. 30 The nonlinear absorption component was estimated under an open aperture.…”

Section: ■ Results and Discussionmentioning

confidence: 92%

“…In order to obtain the second hyperpolarizability data, the concentrations of 2 – 7 in DMF were fixed at 5 × 10 –5 M. A typical trough of normalized transmittance (Figure for 2 and 7 and Figure S6 for 3 – 6 ) reveals that the laser pulses experience a reverse saturable absorption for 2 – 6 and a notable saturable absorption for 7 . That the adsorption pattern of 7 is different from those for 2 – 6 is likely due to its unique structure . Nevertheless, for all of 2 – 7 , the valley-to-peak configuration of the curves of refractive data, evaluated by dividing the normalized Z -scan data obtained under closed aperture by the normalized Z -scan data collected under the open-aperture configuration (Figure for 2 and 7 and Figure S7 for 3 – 6 ), suggests that the nonlinear refractive index change is positive and thus an indication of a strong self-focusing effect …”

Section: Resultsmentioning

confidence: 99%

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Diverse Tp*-Capped W–Cu–S Clusters from One-Pot Assembly Involving in Situ Thiolation of Phosphines

et al. 2016

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In the absence/presence of S8, the one-pot assembly of [Et4N][Tp*WS3] [1; Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate] with [Cu(MeCN)4]PF6 and bis- or tetraphosphine ligands 1,2-bis(diphenylphosphino)ethane (dppe), 1,3-bis(diphenylphosphino)propane (dppp), 1,4-bis(diphenylphosphino)butane (dppb), and N,N,N',N'-tetrakis(diphenylphosphinomethyl)ethylenediamine (dppeda) produces six W-Cu-S clusters, namely, [(Tp*WS3Cu2Cl)2(dppe)] (2), [Tp*WS3Cu4(dppp)2(μ4-Cl)(μ-Cl)]PF6·MeCN (3·MeCN), [(Tp*WS3Cu3)2(μ4-Cl)(μ-Cl)2(dpppS2)] (4), [(Tp*WS3Cu2Cl)2(dppbS2)]·2MeCN·2H2O (5·2MeCN·2H2O), [(Tp*WS3Cu3Cl2)2(dppbS2)] (6), and [(Tp*WS3Cu3)2(Ph2PS2)3(μ6-Cl)0.5](PF6)0.5·0.75CH2Cl2 (7·0.75CH2Cl2). Compounds 2-7 are characterized by elemental analysis, IR, UV-vis, (1)H and (31)P{(1)H} NMR, electrospray ionization mass spectrometry, and X-ray crystallography. For 2, the dppe ligand bridges a pair of butterfly-shaped [Tp*WS3Cu2] cores to form a double-butterfly-shaped structure. For 4, the dppp ligand is susceptible toward S association and forms an in situ generated dpppS2 ligand, supporting an octanuclear double-half-open-cubane structure and contrasting an analogous system wherein a pentanuclear motorcycle-shaped cationic cluster 3 is formed with the absence of S8. A longer dppb ligand readily converts to S-based ligands in 5 and 6, subsequently serving as bridges between a pair of a butterfly-shaped (5) and nest-shaped (6) clusters. Further use of a tetraphosphine ligand, dppeda, in the cluster formation, with the presence of S8, leads to an unexpected ligand degradation to give the [Ph2PS2](-) anions. Three [Ph2PS2](-) anions juxtapose a pair of nest-shaped cluster cores to yield an octanuclear cluster, 7, featuring a cage to encapsulate μ6-Cl(-). The third-order nonlinear-optical (NLO) properties of 2-7 in N,N-dimethylformamide, investigated using a Z-scan technique at 532 nm, show that 2-6 have a reverse saturable absorption, while 7 has a notable saturable absorption. All of 2-7 exhibit a self-focusing effect with hyperpolarizability γ values in the range of 4.71 × 10(-30)-1.02 × 10(-29) esu, which are 440-1000 times higher than that of 1. The formation of 4-7 from 1 through the in situ thiolation of phosphine ligands presents a new approach to the design and assembly of the W-Cu-S clusters with interesting structural arrays and better NLO properties.

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Section: ■ Results and Discussionmentioning

confidence: 92%

Section: Resultsmentioning

confidence: 99%

Diverse Tp*-Capped W–Cu–S Clusters from One-Pot Assembly Involving in Situ Thiolation of Phosphines

et al. 2016

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“…The nonlinear absorptive indices α 2 , the effective third-order NLO refractive indices n 2 and susceptibility χ (3) , as well as the second hyperpolarizability γ of these compounds are acquired through the following equations and are included in Table . In all cases, the n 2 values are positive, indicative of self-focusing effects. − wherein N is the number of molecules per cm 3 , n 0 is the linear refractive index of DMF ( n 0 = 1.43), c is the speed of light, and ω is the optical frequency. It is acceptable to use the γ value as a measure for the NLO performance of neat materials.…”

Section: Resultsmentioning

confidence: 98%

Assembly of [Tp*WS₃Cu₂]-Supported Coordination Polymers from Linkers with a Unique μ-Pyridyl Bridging Mode and Their Enhanced Third-Order Nonlinear Optical Performances

Liu

Zhao

Zhou

et al. 2016

Crystal Growth & Design

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We have prepared a family of [WS 3 Cu 2 ]-based coordination polymers with a rare μ-N type coordination by a simple one-pot assembly of [Et 4 N][Tp*WS 3 ] (1) with CuCN in the presence of pyridine (py), 4,4′-bipyridine (bipy), 1,2-bis(4pyridyl)ethane (bpea), and 2,4,6-tri(4-pyridyl)-1,3,5-triazine (tpt) at room temperature. The resulting coordination polymers [Tp*WS 3 Cu 2 6) share a butterfly-shaped [Tp*WS 3 Cu 2 ] motif with sizable concave to accommodate pyridyl ligands. The approximate mirror symmetry of the motif also induces the orthogonal coalignment of the pyridyl ligands, reinforcing a unique μ-type association with the Cu centers of the cluster skeleton. Such a coordination mode, though scarce in general coordination chemistry, is universal in our series with good ligand tolerance including ligand size and symmetry. In addition, each butterfly-shaped [Tp*WS 3 Cu 2 ] motif is linked by CN (2), Cu(CN) 2 (3), Cu 2 (CN) 5 /μ 4 -bipy (4), CN/μ 4 -bpea (5), and CN/μ 6 -tpt (6) to yield diverse polydimensional structures showing onedimensional zigzag chains (2 and 3), two-dimensional networks (4 and 5), and a three-dimensional net (6). The third-order nonlinear optical (NLO) property of 2−6 in DMF measured using a Z-scan technique at 532 nm demonstrated that 2−6 have a reverse saturable absorption and self-focusing effects with the hyperpolarizability γ values in the range of 6.32 × 10 −30 esu to 9.82 × 10 −30 esu. Such values are remarkably larger than that of their precursor complex 1 (1.07 × 10 −32 esu). The results provide an interesting insight into how the μ-type coordination mode of N-donor ligands affects the self-assembly of the [Tp*WS 3 Cu 2 ]supported coordination polymers and their structural topologies, as well as their third-order NLO performances.

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“…[22][23][24] For the other, the optical films are obtained by doping different molecules using physical methods. [25][26][27] In our previous study, [28] phenoxazinium containing films prepared by sol-gel method was discussed. With increasing reaction mole ratios of phenoxazinium to tetraethylorthosilicate, the third-order nonlinear optical properties transform reverse saturated absorption to saturated absorption, which is similar to this article.…”

Section: Figmentioning

confidence: 99%

Third-order nonlinear optical properties of spin-coating films containing benzo[α]phenoxazinium: from reverse saturated to saturated absorptions

et al. 2015

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Aggregation induced convertible third-order nonlinear optical absorptions of the phenoxazinium containing films prepared by sol–gel method

Cited by 6 publications

References 35 publications

Diverse Tp*-Capped W–Cu–S Clusters from One-Pot Assembly Involving in Situ Thiolation of Phosphines

Diverse Tp*-Capped W–Cu–S Clusters from One-Pot Assembly Involving in Situ Thiolation of Phosphines

Assembly of [Tp*WS₃Cu₂]-Supported Coordination Polymers from Linkers with a Unique μ-Pyridyl Bridging Mode and Their Enhanced Third-Order Nonlinear Optical Performances

Third-order nonlinear optical properties of spin-coating films containing benzo[α]phenoxazinium: from reverse saturated to saturated absorptions

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Aggregation induced convertible third-order nonlinear optical absorptions of the phenoxazinium containing films prepared by sol–gel method

Cited by 6 publications

References 35 publications

Diverse Tp*-Capped W–Cu–S Clusters from One-Pot Assembly Involving in Situ Thiolation of Phosphines

Diverse Tp*-Capped W–Cu–S Clusters from One-Pot Assembly Involving in Situ Thiolation of Phosphines

Assembly of [Tp*WS3Cu2]-Supported Coordination Polymers from Linkers with a Unique μ-Pyridyl Bridging Mode and Their Enhanced Third-Order Nonlinear Optical Performances

Third-order nonlinear optical properties of spin-coating films containing benzo[α]phenoxazinium: from reverse saturated to saturated absorptions

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Assembly of [Tp*WS₃Cu₂]-Supported Coordination Polymers from Linkers with a Unique μ-Pyridyl Bridging Mode and Their Enhanced Third-Order Nonlinear Optical Performances