Organic nanostructures with controllable morphology fabricated from mixed (phthalocyaninato)(porphyrinato) europium double-decker complexes.
The self-assembly behavior of two sandwich-type mixed (phthalocyaninato)(porphyrinato) europium double-decker complexes, namely Eu(Pc)(TClPP) [Pc = phthalocyaninate; TClPP = meso-tetrakis(4-chlorophenyl)porphyrinate] (1) and optically active (R)- and (S)-EuH[Pc(OBNP)(2)](TClPP)] [Pc(OBNP)(2) = phthalocyaninate with two aromatic chiral binaphthayl units attached at the nonperipheral positions] (2), has been comparatively studied. In addition, a hydrophilic additive with intense adhesive ability, sodium carboxymethylcellulose (CMC), was also introduced onto the sandwich-type self-assembly systems to combine with double-decker molecules to induce additional hydrophilic/hydrophobic interaction. In the absence of the additive CMC, the double-decker molecules of 1 self-assemble into nanobelts in mixed solvent of chloroform and methanol. Introduction of two aromatic chiral binaphthayl units onto the nonperipheral positions of phthalocyanine ligand in the sandwich-type mixed double-decker complex 2 leads to the formation of tubal nanostructures. Observation of significant difference in the circular dichroism (CD) spectra of (R)- and (S)-2 in chloroform from their aggregates dispersed in methanol confirms the effective intermolecular interaction due to the interplay of pi-pi interaction between adjacent double-decker molecules with chiral discrimination among chiral side chains at supramolecular level. With addition of CMC, cooperation of intrinsic intermolecular pi-pi interaction with additionally introduced hydrophilic/hydrophobic interaction between adjacent double-decker molecules induces the formation of nanoscale hollow spheres at 45 degrees C during the self-assembly process of 1 and 2.
Zhang
Xiaomei
X
Department of Chemistry, Shandong University, Jinan 250100, China.
Wang
Quanbo
Q
Wu
Lizhen
L
Lv
Wei
W
Lu
Jitao
J
Bian
Yongzhong
Y
Jiang
Jianzhuang
J
D000042:Absorption; D002266:Carboxymethylcellulose Sodium / Q000737:chemistry; D002942:Circular Dichroism; D005063:Europium / Q000737:chemistry*; D057927:Hydrophobic and Hydrophilic Interactions; D007211:Indoles / Q000737:chemistry*; D054833:Isoindoles; D008958:Models, Molecular; D008968:Molecular Conformation; D049329:Nanostructures / Q000737:chemistry*; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D011166:Porphyrins / Q000737:chemistry*; D013055:Spectrophotometry, Infrared; D013237:Stereoisomerism; D013379:Substrate Specificity; D014961:X-Ray Diffraction
D007211:Indoles; D054833:Isoindoles; D009942:Organometallic Compounds; D011166:Porphyrins; D005063:Europium; D002266:Carboxymethylcellulose Sodium; C013647:phthalocyanine