Gas sensing with hexafluoroisopropanol substituted phthalocyanines andvic-dioximes: a comparative study

Abstract

Phthalocyanines (Pcs) are established sensitive materials for chemical gas sensors due to their superb sensing characteristics and the achievable manifold in their analyte interaction properties. Their sorption properties are determined by the metal ion center and substituents attached to the periphery of the ring system. Similarly, vic-dioximes can be modified in their sorption properties and employed as sensitive materials. In this work, a nickel Pc and various vic-dioximes functionalized with the same hexafluoroisopropanol moiety are assessed and compared in their gas-sensing properties using the quartz crystal microbalance for the first time. This specific substituent is selected for its hydrogen bond acidity for strong interactions with analytes having corresponding sites. The synthesis and characterization of the new compounds are described. Sensor results are presented for ten selected organic compounds and the chemical warfare agent simulant dimethyl methylphosphonate (DMMP). Both compound classes exhibit good sensing performance but were found to exhibit very diverging analyte preferences, as preferential sorption of either amines or polar compounds was observed depending on the molecule type. Thus, by applying the same substituent to different base molecules, sensitive compounds with very distinct sensing properties can be realized.

HFIP in Organic Synthesis

“…Besides its use in the preparation of polymers and advanced materials, the elements of HFIP have been incorporated into materials itself. Taking advantage of its slight acidity and hydrogen bonding ability, poisonous gas-sensing materials functionalized with HFIP showed enhancement and preference for sensing basic analytes. , The hexafluoroisopropoxy anion was found to be an essential ligand for the development of efficient, highly conductive, and oxidatively stable electrolytes, Ca­[B­(hfip) 4 ] 2 and Mg­[B­(hfip) 4 ] 2 , paving the way toward the development of new rechargeable calcium- and magnesium-based batteries. − …”

Toward Efficient Toxic-Gas Detectors: Exploring Molecular Interactions of Sarin and Dimethyl Methylphosphonate with Metal-Centered Phthalocyanine Structures

“…The sensitivity of phthalocyanines and porphyrins (i.e., H 2 Pc, CuPc, NiPc, PbPc, ZnPc, TiPc, MnTPP, InTPP) to, e.g., DMMP has been explored in refs ( 38 ) and ( 44 − 48 ). Despite this potential possibility of using phthalocyanines or porphyrins in, e.g., DMMP sensing, only a few studies regarding this topic have been recently published.…”

“…The sensitivity of phthalocyanines and porphyrins (i.e., H 2 Pc, CuPc, NiPc, PbPc, ZnPc, TiPc, MnTPP, InTPP) to, e.g., DMMP has been explored in refs and − . Despite this potential possibility of using phthalocyanines or porphyrins in, e.g., DMMP sensing, only a few studies regarding this topic have been recently published. ,,, There is also a number of theoretical studies on molecular adsorption on phthalocyanines and porphyrins. ,− In this work, we combine density-functional theory (DFT) calculations with X-ray photoelectron spectroscopy (XPS) to provide profound knowledge about the sensing mechanism of sarin and DMMP by ZnPc films.…”