Structure-property relationships in As-S-Se glasses for waveguide applications probed by near-infrared Raman spectroscopy

Author(s):  
Clara Rivero ◽  
Alfons Schulte ◽  
Kathleen Richardson
2020 ◽  
Author(s):  
Alex Stafford ◽  
Dowon Ahn ◽  
Emily Raulerson ◽  
Kun-You Chung ◽  
Kaihong Sun ◽  
...  

Driving rapid polymerizations with visible to near-infrared (NIR) light will enable nascent technologies in the emerging fields of bio- and composite-printing. However, current photopolymerization strategies are limited by long reaction times, high light intensities, and/or large catalyst loadings. Improving efficiency remains elusive without a comprehensive, mechanistic evaluation of photocatalysis to better understand how composition relates to polymerization metrics. With this objective in mind, a series of methine- and aza-bridged boron dipyrromethene (BODIPY) derivatives were synthesized and systematically characterized to elucidate key structure-property relationships that facilitate efficient photopolymerization driven by visible to NIR light. For both BODIPY scaffolds, halogenation was shown as a general method to increase polymerization rate, quantitatively characterized using a custom real-time infrared spectroscopy setup. Furthermore, a combination of steady-state emission quenching experiments, electronic structure calculations, and ultrafast transient absorption revealed that efficient intersystem crossing to the lowest excited triplet state upon halogenation was a key mechanistic step to achieving rapid photopolymerization reactions. Unprecedented polymerization rates were achieved with extremely low light intensities (< 1 mW/cm<sup>2</sup>) and catalyst loadings (< 50 μM), exemplified by reaction completion within 60 seconds of irradiation using green, red, and NIR light-emitting diodes.


2020 ◽  
Vol 235 (6-7) ◽  
pp. 213-223
Author(s):  
Hilke Petersen ◽  
Lars Robben ◽  
Thorsten M. Gesing

AbstractThe temperature-dependent structure-property relationships of the aluminosilicate perrhenate sodalite |Na8(ReO4)2|[AlSiO4]6 (ReO4-SOD) were analysed via powder X-ray diffraction (PXRD), Raman spectroscopy and heat capacity measurements. ReO4-SOD shows two phase transitions in the investigated temperature range (13 K < T < 1480 K). The first one at 218.6(1) K is correlated to the transition of dynamically ordered $P\overline{4}3n$ (> 218.6(1 K) to a statically disordered (<218.6(1) K) SOD template in $P\overline{4}3n$. The loss of the dynamics of the template anion during cooling causes an increase of disorder, indicated by an unusual intensity decrease of the 011-reflection and an increase of the Re-O2 bond length with decreasing temperature. Additionally, Raman spectroscopy shows a distortion of the ReO4 anion. Upon heating the thermal expansion of the sodalite cage originated in the tilt-mechanism causes the second phase transition at 442(1) K resulting in a symmetry-increase from $P\overline{4}3n$ to $Pm\overline{3}n$, the structure with the sodalites full framework expansion. Noteworthy is the high decomposition temperature of 1320(10) K.


1989 ◽  
Vol 173 ◽  
Author(s):  
D.S. Donald ◽  
L.-T. Cheng ◽  
G. Desiraju ◽  
G. R. Meredith ◽  
F. C. Zumsteg

ABSTRACTThe design of molecular crystals with specific optical properties, which are thought to arise from constituent molecules’ polarizability properties, is a desirable but currently unachievable goal. One can partially achieve this goal by choosing compounds with specific molecular attributes and empirically determining the manner in which these are translated into crystal properties. Besides the fact that there are no certain rules for prediction of crystal packing arrangements, there is also a problem in specifying molecular properties from what are today incomplete polarizability structure-property relationships. We have, realizing these limitations, identified new molecular crystals by a nonlinear optical (powder-SHG) scouting-screening program from lists of compounds chosen because of desirable molecular properties. Examination of successful materials has revealed interesting, new alignment motifs. Some of these materials, a set of halogen and cyano derivatives of aromatic compounds, are described relating properties and structures of molecules and crystals. In particular, the orientation directing influence of intermolecular halogen-cyano interactions and the use of heterocyclic compounds to improve transparency in the near infrared and in the blue and near ultraviolet spectral regions are demonstrated.


2020 ◽  
Author(s):  
Alex Stafford ◽  
Dowon Ahn ◽  
Emily Raulerson ◽  
Kun-You Chung ◽  
Kaihong Sun ◽  
...  

Driving rapid polymerizations with visible to near-infrared (NIR) light will enable nascent technologies in the emerging fields of bio- and composite-printing. However, current photopolymerization strategies are limited by long reaction times, high light intensities, and/or large catalyst loadings. Improving efficiency remains elusive without a comprehensive, mechanistic evaluation of photocatalysis to better understand how composition relates to polymerization metrics. With this objective in mind, a series of methine- and aza-bridged boron dipyrromethene (BODIPY) derivatives were synthesized and systematically characterized to elucidate key structure-property relationships that facilitate efficient photopolymerization driven by visible to NIR light. For both BODIPY scaffolds, halogenation was shown as a general method to increase polymerization rate, quantitatively characterized using a custom real-time infrared spectroscopy setup. Furthermore, a combination of steady-state emission quenching experiments, electronic structure calculations, and ultrafast transient absorption revealed that efficient intersystem crossing to the lowest excited triplet state upon halogenation was a key mechanistic step to achieving rapid photopolymerization reactions. Unprecedented polymerization rates were achieved with extremely low light intensities (< 1 mW/cm<sup>2</sup>) and catalyst loadings (< 50 μM), exemplified by reaction completion within 60 seconds of irradiation using green, red, and NIR light-emitting diodes.


2018 ◽  
Vol 90 (14) ◽  
pp. 8576-8582 ◽  
Author(s):  
Kaixiang Zhou ◽  
Yuying Li ◽  
Yi Peng ◽  
Xiaomei Cui ◽  
Jiapei Dai ◽  
...  

Author(s):  
Rocío Estefanía Rojas-Hernandez ◽  
Fernando Rubio-Marcos ◽  
Giulio Gorni ◽  
Carlo Marini ◽  
Mati Danilson ◽  
...  

Development of new near infrared luminescent (NIR) emitters improves our understanding of their fundamental structure–property relationships.


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