Origin of crystallization suppression in a new amorphous molecular white-light-generating material

Klee, Benjamin D.; Paulus, Benedict; Vasco, Jonathan Link; Hosokawa, Saburo; Stellhorn, Jens Rüdiger; Hayakawa, Shinjiro; Dehnen, Stefanie; Pilgrim, W.‐C.

doi:10.1016/j.scriptamat.2022.114851

Cited by 3 publications

(6 citation statements)

References 15 publications

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“…There are persuasive arguments for both views: the cluster dimers studied by DFT simulations [ 10 ] show that inter‐molecular S–S distances should appear in the range 3.5–3.7 Å, depending on the dimer geometry (stacked vs alternating arrangements of the substituents). On the other hand, our recent RMC study on [(PhSn) 4 S 6 ] clusters [ 11 ] finds substantial cluster core distortions, with S–S distances varying broadly between 3.5‐4.2 Å (in addition to inter‐molecular S–S distances also found in the same range).…”

Section: Discussionmentioning

confidence: 98%

“…[16]. ) On the other hand, since our previous studies [ 10,11,15 ] suggest that the inter‐cluster distances may be on the same length scale as (or even smaller than) the intra‐cluster atomic pairs, they fall in the reliable range probed of this method, as do the local distortions of the cluster cores. Therefore, the measurements presented here provide a valuable contribution to the as of yet puzzling physical mechanisms behind the different NLO effects.…”

Section: Introductionmentioning

confidence: 99%

“…A recent study [11] based on X-ray scattering as well as extended X-ray absorption fine structure spectroscopy (EXAFS) data and a reverse Monte Carlo (RMC) modeling procedure, [12,13] investigated the local structure of the [(PhSn) 4 S 6 ] compound, which was one of the first examples of this class of compounds exhibiting WLG. [2] Substantial distortions of the heteroadamantane cluster cores were found, which were identified as being responsible for the tendency of the molecules to suppress crystal formation, and are therefore an important feature of the WLG effect.…”

Section: Introductionmentioning

confidence: 99%

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Local Cluster Distortions in Amorphous Organotin Sulfide Compounds and Their Influence on the Nonlinear Optical Properties

Stellhorn

Hayakawa

Klee

et al. 2022

Advanced Optical Materials

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The local structure of four amorphous organotin sulfide compounds is investigated by X‐ray absorption spectroscopy. These compounds exhibit a nonlinear optical (NLO) response upon irradiation with a continuous‐wave near‐infrared laser. Their basic structural motif is a hetero‐adamantane cluster with different organic substituent, but depending on the morphology of the compound and the choice of the organic substituent, the nature of the NLO response changes to either a second harmonic generation or the generation of a supercontinuum, potentially appearing as white light. The structural results provide an experimental evidence that the nature of the NLO properties is tied to distortions occurring at the cluster core, with almost ideal clusters in compounds that show second harmonic generation, and strongly distorted clusters in the case of compounds that generate a supercontinuum. These distortions may enable a closer proximity of the cluster cores, altering the intermolecular order, and thereby influencing the NLO response.

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Section: Discussionmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Local Cluster Distortions in Amorphous Organotin Sulfide Compounds and Their Influence on the Nonlinear Optical Properties

Stellhorn

Hayakawa

Klee

et al. 2022

Advanced Optical Materials

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“…Using a stoichiometric ratio, the formation of coordination polymers has been reported. Reactions with the iron carbonyl [Fe(CO)5] can similarly be carried out, but proceed much slower and at higher temperatures (653)(654)(655)(656). [351,353] [P4S10] (657, Figure 14) is most easily obtained from the elements using method A, though many methods are available.…”

Section: Chemical Science Accepted Manuscriptmentioning

confidence: 99%

Adamantane-type clusters: compounds with a ubiquitous architecture but a wide variety of compositions and unexpected materials properties

Rinn,

Rojas-León,

Peerless

et al. 2024

Chem. Sci.

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“…For the subsequent RMC modeling the experimental x-ray S(Q)s and EXAFS-χ(k)s were used as experimental boundary conditions to which the corresponding functions calculated from the simulated structures should ideally converge. We used a dynamic simulation approach where in addition to molecular moves sulfur and tin atoms were allowed to slightly vary their coordinates inside the cluster-cores within certain limits as described in a previous publication [19].…”

Section: M-rmc Simulationsmentioning

confidence: 99%

Structure determination in a new type of amorphous molecular solids with different nonlinear optical properties: a comparative structural analysis

Vasco¹,

Stellhorn²,

Klee³

et al. 2023

J. Phys.: Condens. Matter

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The microscopic structures of two amorphous molecular solids with extremely nonlinear optical properties have been studied. They consist of organotetrel chalcogenide clusters with the chemical formula [(RSn)4S6]. The basic molecular building blocks are adamantane-like {Sn4S6} cores with organic ligands R attached to the Sn atoms. While the material equipped with R=naphthyl generates frequency doubling upon irradiation with a simple infrared laser diode, the material decorated with R=phenyl responds by emitting brilliant white light. The structural differences were investigated using x-ray scattering and extended x-ray absorption fine structure combined with molecular Reverse Monte Carlo. Transmission electron microscopy and scanning precession electron diffraction were used to examine structural differences from mesoscopic down to microscopic scales. Characteristic differences were found on all scales. While close core-to-core distances between {Sn4S6} cluster cores and molecular distortions are found in the white light emitting material, undistorted molecules and significantly larger core distances characterize the material showing frequency doubling. Here however, results of scanning precession electron diffraction reveal the formation of nanocrystalline structures in the amorphous matrix, which we identify as cause for the suppression of white light emission.

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Origin of crystallization suppression in a new amorphous molecular white-light-generating material

Cited by 3 publications

References 15 publications

Local Cluster Distortions in Amorphous Organotin Sulfide Compounds and Their Influence on the Nonlinear Optical Properties

Local Cluster Distortions in Amorphous Organotin Sulfide Compounds and Their Influence on the Nonlinear Optical Properties

Adamantane-type clusters: compounds with a ubiquitous architecture but a wide variety of compositions and unexpected materials properties

Structure determination in a new type of amorphous molecular solids with different nonlinear optical properties: a comparative structural analysis

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