Effects of metal–ligand coordination on the self-assembly behaviour of a crown ether functionalised perylenetetracarboxylic diimide

A novel perylenetetracarboxylic diimide (PDI) derivative, N,N′-di(4′-benzo-15-crown-5-ether)-1,7-di(4-tert-butyl-phenoxy)perylene-3,4;9,10-tetracarboxylic diimide (CRPDI), has been synthesised and characterised. Dimerisation of CRPDI is induced by the presence of K+ in CHCl3 or spontaneously occurs in methanol, as revealed by absorption and emission spectroscopy. In particular, the formation of co-facial dimer in the presence of K+ proceeds in a three-stage process, as indicated by absorption spectroscopy. The belt- and rope-like nanostructures of CRPDI fabricated from methanol and CHCl3 solution in the presence of K+ are obtained by scanning electron microscopy. Furthermore, the conductivi…

Cation-induced self-assembly of an amphiphilic perylene diimide derivative in solution and Langmuir–Blodgett films

Abstract A novel amphiphilic perylenetetracarboxylic diimide (PDI) derivative, N-(4′-benzo-15-crown-5-ether)-N-hexyl-1,7-di(4-tert-butyl-phenoxy)perylen-3,4,9,10-tetracarboxylic diimide (15C5PDI), has been synthesized and characterized. Dimerization of 15C5PDI is induced in CHCl 3 solution with the present of K + , resulting in the formation of the slipped co-facial J -aggregates, as revealed by absorption and fluorescence spectroscopies. Analysis of the surface pressure–area ( π – A ) isotherms and spectral change for the monolayer formed at the air/water interface, disclosed that 15C5PDI molecules adopted the H -type aggregation mode with a face-to-face configuration and edge-on orientati…

Self-assembled aggregates of amphiphilic perylene diimide-based semiconductor molecules: effect of morphology on conductivity.

Abstract Two amphiphilic perylenetetracarboxylic diimide derivatives modified with different side chains at imide nitrogen, N- n -hexyl-N′-(2-hydroxyethyl)-1,7-di(4′-t-butyl)phenoxy-perylene-3,4:9,10-tetracarboxylic diimide ( PDI 1 ) and N,N′-di(2-hydroxyethyl)-1,7-di(4′-t-butyl)phenoxy-perylene-3,4:9,10-tetracarboxylic diimide ( PDI 2 ), were fabricated into organic nanostructures via solution-phase self-assembly. Their self-assembling properties in methanol and n -hexane have been comparatively studied by electronic absorption, fluorescence, and Fourier transform infrared spectroscopy (FT-IR). The morphologies and structures of the self-assemblies were examined by scanning electronic micr…

The lower rather than higher density charge carrier determines the NH 3 -sensing nature and sensitivity of ambipolar organic semiconductors

International audience; Despite the extensive studies and great application potentials, the sensing nature of ambipolar organic semiconductor gas sensors still remains unclarified, unlike their inorganic counterparts. Herein, different numbers of thiophenoxy groups are introduced into the phthalocyanine periphery of bis(phthalocyaninato) rare earth semiconductors to continuously tune their HOMO and LUMO energies, resulting in the ambipolar M[Pc(SPh)(8)](2) [M = Eu (1), Ho (2)] and p-type M(Pc)[Pc(SPh)(8)] [M = Eu (3), Ho (4)]. An OFET in combination with direct I-V measurements over the devices from the self-assembled nanostructures of 1-4 revealed the original electron and hole densities (…

Facile approaches to build ordered amphiphilic tris(phthalocyaninato) europium triple-decker complex thin films and their comparative performances in ozone sensing

Solution processed thin films of an amphiphilic tris(phthalocyaninato) rare earth triple-decker complex, Eu(2)[Pc(15C5)(4)](2)[Pc(OC(10)H(21))(8)], have been prepared from three different methods: self-assembly (SA) annealed in solvent vapor, quasi-Langmuir-Shäfer (QLS) and drop casting methods. In particular, we successfully developed a simple QLS process for fabricating ordered multilayers with a good thickness control. The films prepared from three different methods were characterized by a wide range of methods including electronic absorption spectra, IR, X-ray diffraction, atomic force microscopy (AFM), and current-voltage (I-V) measurements. J-type aggregates have been formed with the …

Two-Step Solution-Processed Two-Component Bilayer Phthalocyaninato Copper-Based Heterojunctions with Interesting Ambipolar Organic Transiting and Ethanol-Sensing Properties

International audience; The two-component phthalocyaninato copper-based heterojunctions fabricated from n-type CuPc(COOC8H17)(8) and p-type CuPc(OC8H17)(8) by a facile two-step solution-processing quasi-Langmuir-Shafer method with both n/p- and p/n-bilayer structures are revealed to exhibit typical ambipolar air-stable organic thin-film transistor (OTFT) performance. The p/n-bilayer devices constructed by depositing CuPc(COOC8H17)(8) film on CuPc(OC8H17)(8) sub-layer show superior OTFT performance with hole and electron mobility of 0.11 and 0.02 cm(2) V-1 s(-1), respectively, over the ones with n/p-bilayer heterojunction structure with the hole and electron mobility of 0.03 and 0.016 cm(2) …

Tuning the semiconducting nature of bis(phthalocyaninato) holmium complexes via peripheral substituents

The semiconducting properties of the heteroleptic and homoleptic bis(phthalocyaninato) holmium complexes bearing electron-withdrawing phenoxy substituents at the phthalocyanine periphery, namely Ho(Pc)[Pc(OPh)8] (1) and Ho[Pc(OPh)8]2 (2) [Pc = unsubstituted phthalocyaninate; Pc(OPh)8 = 2,3,9,10,16,17,23,24-octaphenoxyphthalocyaninate] have been investigated comparatively. Using a solution-based Quasi–Langmuir–Shafer (QLS) method, the thin solid films of the two compounds were fabricated. The structure and properties of the thin films were investigated by UV-vis absorption spectra, X-ray diffraction (XRD) and atomic force microscopy (AFM). Experimental results indicated that H-type molecular…

Differential study of substituted and unsubstituted cobalt phthalocyanines for gas sensor applications

Abstract The conductivity of CoPc (cobalt phthalocyanine) and Co[(SO3Na)2,3Pc] was measured under a flow of two different gases (NH3 and O3), during exposure/recovery cycles. It appears that the relative responses are linearly related to the concentration, in the 20–200 ppb range for O3 and in the 20–200 ppm range for NH3. Observed during time, the sensing parameters allow a qualitative understanding of the kinetics. The comparative study of those products under both different gases gave interesting results for sensor applications. Whereas CoPc is sensitive to both gases, its sulfonated counterpart is only sensitive to NH3.

Morphology controlled nano-structures of an octa(phenoxy)-substituted phthalocyaninato zinc complex: solvent effect on the self-assembly behaviour

The 2,3,9,10,16,17,24,25-octakis(phenoxy)phthalocyaninato zinc, (Zn[Pc(OPh)8]) was fabricated into nano-/micro-structures via solution-phase self-assembly. The self-assembling properties of Zn[Pc(OPh)8] in coordinating and non-coordinating solvents (methanol and n-hexane) have been comparatively studied by electronic absorption, fluorescence, Fourier transform infrared spectroscopy (FT-IR), scanning electronic microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) techniques. The conducting properties were evaluated by current–voltage (I–V) measurements. Due mainly to the presence of different intermolecular Zn–O coordination interactions between the Zn[Pc(OPh)…

Thin-Film Transistors: Two-Step Solution-Processed Two-Component Bilayer Phthalocyaninato Copper-Based Heterojunctions with Interesting Ambipolar Organic Transiting and Ethanol-Sensing Properties (Adv. Mater. Interfaces 16/2016)

Solution-processed thin films based on sandwich-type mixed (phthalocyaninato)(porphyrinato) europium triple-deckers: Structures and comparative performances in ammonia sensing

The solution-processed thin films of a series of three sandwich-type mixed (phthalocyaninato)(porphyrinato) europium complexes with different numbers of hydroxyl groups at the meso-substituted phenyl groups of porphyrin ligand 1–3 were prepared by a quasi-Langmuir–Shafer (QLS) method. Examination by spectroscopic methods revealed that J-type aggregates have been formed with the increasing degree of order of molecular stacking 1 < 2 < 3 films. The IR and XRD results reveal that, a dimeric supramolecular structure was formed depending mainly on the π–π interaction between the tetrapyrrole cores of neighboring triple-decker molecules, which, as the building blocks, self-assembled into the targ…

Enhanced chemosensing of ammonia based on the novel molecular semiconductor-doped insulator (MSDI) heterojunctions

Abstract A series of new molecular semiconductor-doped insulator (MSDI) heterojunctions as conductimetric transducers to NH3 sensing were fabricated based on a novel semiconducting molecular material, an amphiphilic tris(phthalocyaninato) rare earth triple-decker complex, Eu2[Pc(15C5)4]2[Pc(OC10H21)8], quasi-Langmuir–Shafer (QLS) film, as a top-layer, and vacuum-deposited and cast film of CuPc as well as copper tetra-tert-butyl phthalocyanine (CuTTBPc) QLS film as a sub-layer, named as MSDIs 1, 2 and 3, respectively. MSDIs 1–3 and respective sub-layers prepared from three different methods were characterized by X-ray diffraction, electronic absorption spectra and current–voltage (I–V) measu…