A Spin‐Active, Electrochromic, Solvent‐Free Molecular Liquid Based on Double‐Decker Lutetium Phthalocyanine Bearing Long Branched Alkyl Chains

Abstract

Synthesis and characterization of a novel, multifunctional, solvent-free room-temperature liquid based on alkylated double-decker lutetium(III) phthalocyanine (Pc Lu) are described. Lowering of the melting point and viscosity of intrinsically solid Pc Lu compounds has been achieved through the attachment of flexible, bulky, and long branched-alkyl chains, that is, thio-2-octyldodecyl, to the periphery of the Pc Lu unit. The embedded Pc Lu unit maintains its inherent molecular functions, such as spin-active nature and electrochromic behavior in the liquid state. Comparison of the properties with a solid-like Pc Lu derivative, functionalized with shorter alkyl chains, that is, thio-2-ethylhexyl, underlines the importance of the hampering effect on the π-π interactions of neighboring Pc Lu molecules by bulkier and longer branched-alkyl chains. This study could possibly pave the way for novel multifunctional liquids whose spin-activities are associated with their rheological or optoelectronic properties.

Circularly Polarized Luminescence from Solvent‐Free Chiral Organic π‐Liquids

“…Furthermore, the X‐ray diffraction (XRD) of the Nap1 – Nap4 was investigated, as shown in Figure S1b. The wide halos could be attributed to the average distance between naphthalene units (13.5 Å) as well as chiral alkyl chains in the molten state (4.6 Å) for Nap1 – Nap3 liquids at room temperature, which proves that no long‐range ordered supramolecular assembly is formed in Nap1 – Nap3 liquids, like most of the reported organic liquid systems, [5b, 12–20] while Nap4 has the typical powder sharp peaks patterns.…”

“…It is a general method to introduce branched alkyl side‐chains to the π‐core for preventing the interaction between the π‐units and effectively lowering the glass transition temperature to facilitate the π‐liquid [6–20] . Although most of these branched alkyl chains contain the chiral carbon center, the racemic ones were often employed.…”

Solvent-Free Conjugated Polymer Fluids with Optical Functions

“…Several fluid π-conjugated small molecules reported so far are known to have the same optical properties as those of dilute solutions. [1][2][3][4][5][6][7][8][9] However, it was not clear whether this consistency of optical properties could be maintained in the CP solid and fluid states, or in the rubber state in between.…”

“…Semiconducting LCs have common molecular architecture: rigid π-conjugated units with soft side chains. Over the last decade, our group [1][2][3][4][5][6][7][8][9] and many others [10][11][12][13][14][15][16][17][18][19][20][21][22][23] have inherited this molecular design concept and focused not only on the highly ordered, supramolecular self-assembled structure, but also on the disordered and fluid properties under precisely controlled intermolecular interactions.…”

Synthesis and effect of substituent position, metal type on the electrochemical properties of (3-morpholin-4-ylpropoxy) groups substituted cobalt, manganese phthalocyanines

“…Phthalocyanines and their derivatives have been used in many applications such as chemical and biosensor [3], solar cell, [4,5], catalyst [6], nonlinear optic [7], liquid crystal [8], catalyst [9,10], photosensitizers in photodynamic therapy (PDT) [11,12], because they have intense blue-green colour owing to the electronic delocalization of their 18π electrons. On the other hand, electrochemical characterization of phthalocyanines is important for the electrocatalyst [13], electrosensing [14], electropolymerization [15,16], electrochromic fields [17].…”