Conductive Directly Fused Poly(Porphyrin) Coatings by Oxidative Chemical Vapour Deposition - From Single- to Triple-Fused

Atmospheric pressure plasma polymerisation of metalloporphyrins containing mesoporous membranes for gas sensing applications

Abstract Metalloporphyrins are embedded in an organosilicon matrix by an easily up-scalable atmospheric pressure dielectric barrier discharge method. The integrity of the metalloporphyrins, followed by UV–visible spectroscopy, is successfully preserved and their aggregation prevented. The single molecule properties, rather than the bulk ones, are thus enhanced. Exposure to triethylamine, which reaches the metalloporphyrins through the pores of the organosilicon membrane, led to a shift in the absorption spectrum and confirms the gas sensing potential of such coatings.

Molecular Engineering of Porphyrin‐Tapes/Phthalocyanine Heterojunctions for a Highly Sensitive Ammonia Sensor

International audience; Modulating the interfacial charge alignments by molecular engineering in an organic heterojunction device is a smart strategy to improve its conductivity, which can be exploited in high performance gas sensors development. Herein, the fabrication of new organic heterojunction devices based on porphyrin tapes and phthalocyanines and their potentiality in ammonia sensing at different relative humidity (rh) are investigated. The devices are built using dry approach relying on oxidative chemical vapor deposition for simultaneous synthesis, doping and deposition of the porphyrin tape layer and physical vapor deposition of phthalocyanine layer. The association of the porph…

Constitution and conductivity of metalloporphyrin tapes

Metal–organic covalent network chemical vapor deposition for gas separation

The chemical vapor deposition (CVD) polymerization of metalloporphyrin building units is demonstrated to provide an easily up-scalable one-step method toward the deposition of a new class of dense and defect-free metal–organic covalent network (MOCN) layers. The resulting hyper-thin and flexible MOCN layers exhibit outstanding gas-separation performances for multiple gas pairs.

A new class of ZnIIand CrIIIporphyrins incorporated into porous polymer matrices via an atmospheric pressure plasma enhanced CVD to form gas sensing layers

Designed ZnII and CrIII porphyrins (ZnIIP, CrIIIP(Cl)(H2O)) and conventional ZnIITPP and CrIIITPP(Cl)(H2O) are immobilized into porous polysiloxane films via chemical vapor deposition enhanced by an atmospheric pressure dielectric barrier discharge. UV/vis spectroscopy and mass spectrometry prove the integrity of the chromophores after the plasma treatment. The optical amine sensing capabilities of the films are investigated spectroscopically on exposure to triethylamine vapors. A series of coatings with different porphyrin loadings indicate influences of the deposition conditions on the growth of the sensing films and hence the device performance. Additionally, the synthesis and characteri…

Molecular flattening effect to enhance the conductivity of fused porphyrin tape thin films.

The straightforward synthesis of directly fused porphyrins (porphyrin tapes) from 5,15-diphenyl porphyrinato nickel(II) complexes with different substituents on the phenyl rings is achieved while processing from the gas phase. The porphyrin tapes, exhibiting NIR absorption, are readily obtained in thin film form. The gas phase approach cuts the need for solubilizing groups allowing for the first time the study of their conductivity according to the substituent. 2-Point probe and conductivity AFM measurements evidence that reducing the size of the meso substituents, phenyl < mesityl < di(3,5-tert-butyl)phenyl < di(2,6-dodecyloxy)phenyl, improves the thin film conductivity by several orders o…

Reactivity of Nickel(II) Porphyrins in oCVD Processes—Polymerisation, Intramolecular Cyclisation and Chlorination

Abstract Oxidative chemical vapour deposition of (5,15‐diphenylporphyrinato)nickel(II) (NiDPP) with iron(III) chloride as oxidant yielded a conjugated poly(metalloporphyrin) as a highly coloured thin film, which is potentially useful for optoelectronic applications. This study clarified the reactive sites of the porphyrin monomer NiDPP by HRMS, UV/Vis/NIR spectroscopy, cyclic voltammetry and EPR spectroscopy in combination with quantum chemical calculations. Unsubstituted meso positions are essential for successful polymerisation, as demonstrated by varying the porphyrin meso substituent pattern from di‐ to tri‐ and tetraphenyl substitution. DFT calculations support the proposed radical oxi…

Plasma Polymer Membranes for Immobilising Metalloporphyrins

Atmospheric pressure dielectric barrier discharge formation of organosilicon thin films loaded with zinc 5,10,15,20-tetraphenylporphyrin (Zn(TPP)) was investigated for different deposition conditions. UV–visible spectroscopy and scanning electron microscopy revealed the effects of the metalloporpyhrins injection parameters and the plasma polymerisation conditions can affect the dispersion of the metalloporphyrins and the morphology of the coatings. The stability of the embedded Zn(TPP) molecules was investigated by orbitrap mass spectrometry.

αα- and αβ-Zinc-meso-A2B2-tetraarylporphyrins with large optical responses to triethylamine

Synthesis and separation of αα- and αβ-meso-A(2)B(2)-zinc(II) tetraarylporphyrin atropisomers with A = mesityl and B = ortho-phenylethynyl-phenyl are reported. Both isomers exhibit large optical responses upon axial NEt(3) coordination which are visible to the human eye and could therefore be beneficial for the design of smart amine sensing materials. The larger spectral changes as compared to Zn(TPP) are attributed to pronounced distortions of the porphyrin π-system due to steric interactions of the coordinating amine with the porphyrin periphery. This effect as well as the coordination site of NEt(3) at the αα-isomer have been studied by NMR experiments and were rationalized by DFT calcul…

Conductive Fused Porphyrin Tapes on Sensitive Substrates by a Chemical Vapor Deposition Approach.

Abstract Oxidative polymerization of nickel(II) 5,15‐diphenyl porphyrin and nickel(II) 5,15‐bis(di‐3,5‐tert‐butylphenyl) porphyrin by oxidative chemical vapor deposition (oCVD) yields multiply fused porphyrin oligomers in thin film form. The oCVD technique enables one‐step formation, deposition, and p‐doping of conjugated poly(porphyrins) coatings without solvents or post‐treatments. The decisive reactions and side reactions during the oCVD process are shown by high‐resolution mass spectrometry. Owing to the highly conjugated structure of the fused tapes, the thin films exhibit an electrical conductivity of 3.6×10−2 S cm−1 and strong absorption in the visible to near‐infrared spectral regio…

Dual application of (aqua)(chlorido)(porphyrinato)chromium(III) as hypersensitive amine-triggered ON switch and for dioxygen activation.

Although synthesis and substitution reactions of chlorido chromium(III) porphyrins Cr(III)(TPP)(Cl)(L) (H2TPP = 5,10,15,20-tetraphenyl porphyrin, L = pyridine, H2O, ROH, etc.), have been well-established in coordination chemistry for decades, an unexpected dichotomous reactivity of Cr(III)(TPP)(Cl)(H2O) (1) toward amines is disclosed here. This reactivity leads to the application of 1 as highly sensitive substoichiometric and irreversible ON switch for amine detection by an autocatalytic pathway. The concomitant activation of O2 by the 1/amine system is furthermore exploited in an electrochemically driven epoxidation of norbonene using O2 as initial oxidant.

Gas Selective Ultrathin Organic Covalent Networks Synthesized by iPECVD: Does the Central Metal Ion Matter?

The potential of porphyrin-derived metal organic covalent networks (OCN) thin films on light gas separations has been recently demonstrated. However, whether or not the central metal ion of the porphyrin plays a key role on separation performance has yet to be elucidated. Here, one metal-free and three metal-containing (zinc(II), manganese(III), and cobalt(II)) porphyrin-derived OCN thin films are successfully deposited on various substrates via an easily scalable initiated plasma-enhanced chemical vapor deposition approach. Among these four porphyrin-derived OCN thin films exhibiting superior light gas separation performances, three of them are synthesized for the first time. The gas perme…

Gas Separation: Metal-Organic Covalent Network Chemical Vapor Deposition for Gas Separation (Adv. Mater. 34/2016)

Front Cover: Constitution and Conductivity of Metalloporphyrin Tapes (Eur. J. Inorg. Chem. 20/2020)

Optical sensing responses of CrIIICl(TPP)(H2O)-based coatings obtained by an atmospheric pressure plasma method – Application to the detection of volatile amines

Food spoilage processes are a considerable concern for both the food industry and the consumer, due to financial, food quality and food safety aspects. A primary issue is the prevention/monitoring of the formation of biogenic and volatile amines, such as occurring in fish and in other microbiologically unstable food items rich in proteins, produced by e.g. oxidative decarboxylation of amino acids. One strategy for their monitoring is the development of films with colorimetric sensing properties that are able to indicate food spoilage. The aim of this investigation was the development of a novel metalloporphyrin-based coating allowing the sensitive detection of typical volatile amines, such …