Coordination polymers (CPs) and coordination network solids such as metal-organic frameworks (MOFs) have gained increasing interest during recent years due to their unique properties and potential applications. Preparing 3D printed structures using CP would provide many advantages towards utilization in fields such as catalysis and sensing. So far, functional 3D structures were printed mostly by dispersing pre-synthesized particles of CPs and MOFs within a polymerizable carrier. This resulted in a CP active material dispersed within a 3D polymeric object, which may obstruct or impede the intrinsic properties of the CP. Here, we present a new concept for obtaining 3D free-standing objects solely composed of CP material, starting from coordination metal complexes as the monomeric building blocks, and utilizing the 3D printer itself as a tool to in situ synthesize a coordination polymer during printing, and to shape it into a 3D object, simultaneously. To demonstrate this, a 3D-shaped nickel tetraacrylamide monomeric complex composed solely of the CP without a binder was successfully prepared using our direct print-and-form approach. We expect that this work will open new directions and unlimited potential in additive manufacturing and utilization of CPs.
Low‐frequency Raman (LFR) spectroscopy is a powerful, nondestructive method used for chemical and structural characterization of materials. Typically, the signal intensity of LFR is relatively low, resulting significantly longer signal acquisition duration. Here, we show a photonic structure based on a planar optical microcavity consists of two distributed Bragg reflectors that is capable of enhancing the LFR signal of the material placed in between the mirrors. CsPbI3 forms smooth and uniform thin films and has distinct LFR signatures; thus, we chose to use it for investigating the microcavity enhancement capabilities. By compromising the quality factor of the cavity, we achieved a broader transmission peak and essentially earned enhancement from the double‐resonance effect. Measurements on a CsPbI3 thin film inside a cavity compared with a bare film spin coated on glass demonstrated two orders of magnitude enhancement. In addition, we fabricated the microcavity with a gradient in the resonance wavelength, in order to study the tuning effect on spectral features and on the enhancement factor. Our results show that microcavity is a promising device for enhancing LFR scattering signal and for sensitive characterization of nanomaterials.
Long-range structures and dynamics are central to coordination chemistry, yet are hard to identify experimentally. By combining polarized low-frequency Raman spectroscopy with single crystal XRD to study barium nitrilotriacetate, a...
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