Second harmonic generation microscopy reveals hidden polar organization in fluoride doped MIL-53(Fe)

Polar metal–organic frameworks have potential applications as functional non-linear optical, piezoelectric, pyroelectric and ferroelectric materials. Using second harmonic generation microscopy we found that fluoride doping of the microporous iron(III) terephthalate MOF MIL-53(Fe) induces a polar organization in its structure, which was not previously detected with XRD. The polar order is only observed when both fluoride and guest molecules are present, and may be related to a complex interplay between the adsorbates and the framework, leading to a modification of the positioning of fluoride in the inorganic Fe-chains. Combined polarized second harmonic generation microscopy and scanning pyroelectric microscopy show that the polar axis is unidirectional and of the same sense over the whole crystal, extending up to 100 micrometers. This finding shows how MOF materials can be endowed with useful properties by doping MOFs with fluoride.Chemical EngineeringApplied Science

Nonlinear optical probes of nucleation and crystal growth: recent progress and future prospects

In situexperimental studies have been key in uncovering the often elusive pathways of nucleation and crystal growth. In the field of material science and medicine this offers the prospect of controlling crystallization processes to fight disease or tailor materials towards specific applications. To further advance this quest there is a need for flexible techniques mapping the different stages of crystallization with maximal sensitivity. This article reviews the benefits of nonlinear optical techniques to take on this challenge. We provide a perspective on various nucleation and crystal growth studies that were carried out by nonlinear optical probing techniques. A theoretical background is established, different relevant nonlinear optical phenomena are defined, and optical setups that have been used by various authors are summarized. A primary focus is demonstrating the benefits of nonlinear optical techniques for thein situstudy of crystallization. These benefits include low detection limits, complementary information by combining second- and third-order techniques, as well as relatively simple bench-top setups. Through microscopy, high contrast imaging of concomitant formations can moreover be achieved. The discussion outlines several studies involving ionic compounds, noble metal nanoparticles, polymers, metal organic frameworks and pharmaceutical compounds. Finally, we discuss future evolutions in nonlinear optical probing that are expected to further advance the field.ChemE/Catalysis Engineerin

Poly(3-alkylthiophene)s show unexpected second-order nonlinear optical response

Regioregular poly(3-hexylthiophene)s with chain lengths varying from 5 to 100 monomers are synthesized. Poly(3-hexylthiophene)s show in solution an unexpectedly significant second-order nonlinear optical response. The increase in transition dipole moment upon oligomerisation causes the significant second-order nonlinear optical response.Chemical EngineeringApplied Science