A Stable Antiaromatic 5,20‐Dibenzoyl [28]Hexaphyrin(1.1.1.1.1.1): Core AuIII Metalation and Subsequent Peripheral BIII Metalation

5,20‐Dibenzoyl [28]hexaphyrin(1.1.1.1.1.1) was synthesized as the first hexaphyrin bearing meso‐aroyl substituents. The meso‐dibenzoyl substituents are hydrogen‐bonded with the pyrrolic protons to stabilize an antiaromatic dumbbell conformer. Core metalation of this hexaphyrin with Au^III afforded rectangular and aromatic [26]hexaphyrin bis‐Au^III complexes, the major isomer of which was reduced with NaBH₄ to give its antiaromatic 28π bis‐Au^III complex. This complex allowed facile peripheral metalation with B^III owing to the peripheral benzoyl substituents.     

Axially Dissymmetric Chiral (R)‐N,W‐Bis(2‐hydroxy‐3,5‐ditert‐butyl‐arylmethyl)‐1, 1′‐binaphthalene‐2,2′‐diamine as Chiral Ligands in the Reaction of Diethylzinc to Aldehydes†

Chiral ligand (A)‐N,N′‐Bis(2‐hydroxy‐3,5‐di‐tert‐butyl‐arylmethyl)‐1,1′‐binaphthalene‐2,2′‐diamine derived from the reduction of Schiff base (R)‐2,2′‐bis (3,5‐di‐tert‐butyl‐2‐hydroxybenzylideneamino)‐1, 1′‐binaphthyl with LiAlH₄, is fairly effective in the asymmetric addition reaction of diethylzinc to aldehydes by which good yields (46%‐94%) of the corresponding sec‐alcohols can be obtained in moderate ee (51%‐79%) with R configuration for a variety of aldehydes.     

Di‐tert‐butyl ketone hydrazone and di‐tert‐butyl ketone triphenyl­phosphoranyl­idene­hydrazone

Reaction of di‐tert‐butyl ketone with hydrazine hydrate gives di‐tert‐butyl ketone hydrazone, C₉H₂₀N₂, which is dimerized by double hydrogen bonding in the solid state. Further reaction of this compound with dibromo­triphenyl­phospho­rane gives di‐tert‐butyl ketone triphenyl­phosphoranyl­idene­hydrazone, C₂₇H₃₃N₂P, in the structure of which double chains parallel to the c axis are formed through weak C—H⋯π and π–π stacking inter­actions. The hydrazone group is nearly planar in both cases. In the second compound, one of the aromatic rings is nearly coplanar with the hydrazone moiety, indicating possible π‐conjugation.     

meso‐3,5‐Bis(trifluoromethyl)phenyl‐Substituted Expanded Porphyrins: Synthesis,Characterization, and Optical,Electrochemical, and Photophysical Properties

Trifluoroacetic acid‐catalyzed condensation of pyrrole with electron‐deficient and sterically hindered 3,5‐bis(trifluoromethyl)benzaldehyde results in the unexpected production of a series of meso‐3,5‐bis(trifluoromethyl)phenyl‐substituted expanded porphyrins including [22]sapphyrin 2 , N‐fused [22]pentaphyrin 3 , [26]hexaphyrin 4 , and intact [32]heptaphyrin 5 together with the conventional 5,10,15,20‐tetrakis(3,5‐bis(trifluoromethyl)phenyl)porphyrin 1 . These expanded porphyrins are characterized by mass spectrometry, ¹H NMR spectroscopy, UV/Vis/NIR absorption spectroscopy, and fluorescence spectroscopy. The optical and electrochemical measurements reveal a decrease in the HOMO–LUMO gap with increasing size of the conjugated macrocycles, and in accordance with the trend, the deactivation of the excited singlet state to the ground state is enhanced.     

5,20‐Bis(ethoxycarbonyl)‐Substituted Antiaromatic [28]Hexaphyrin and Its Bis‐NiII and Bis‐CuII Complexes

5,20‐Bis(ethoxycarbonyl)‐[28]hexaphyrin was synthesized by acid catalyzed cross‐condensation of meso‐diaryl‐substituted tripyrrane and ethyl 2‐oxoacetate followed by subsequent oxidation. This hexaphyrin was found to be a stable 28π‐antiaromatic compound with a dumbbell‐like conformation. Upon oxidization with PbO₂, this [28]hexaphyrin was converted into an aromatic [26]hexaphyrin with a rectangular shape bearing two ester groups at the edge side. The [28]hexaphyrin can incorporate two Ni^II or Cu^II metals by using the ester carbonyl groups and three pyrrolic nitrogen atoms to give bis‐Ni^II and bis‐Cu^II complexes with essentially the same dumbbell‐like structure. The antiaromatic properties of the [28]hexaphyrin and its metal complexes have been well characterized.     

Highly Chemo‐, Regio‐, and Enantioselective Rhodium‐Catalyzed Cross‐Cyclotrimerization of Two Different Alkynes with Alkenes

It has been established that a cationic rhodium(I)/(R)‐tol‐binap complex catalyzes the cross‐cyclotrimerization of silylacetylenes, di‐tert‐butyl acetylenedicarboxylates, and acrylamides with excellent chemo‐, regio‐, and enantioselectivities. Unsymmetrical alkynoates can also be employed in place of di‐tert‐butyl acetylenedicarboxylate for this process, but with reduced chemoselectivity.     

Structural investigation of one‐ and two‐dimensional coordination polymers based on cobalt–bis(dioxolene) units and 1‐hydroxy‐1,2,4,5‐tetrakis(pyridin‐4‐yl)cyclohexane

The combination of cobalt, 3,5‐di‐tert‐butyldioxolene (3,5‐dbdiox) and 1‐hydroxy‐1,2,4,5‐tetrakis(pyridin‐4‐yl)cyclohexane (tpch) yields two coordination polymers with different connectivities, i.e. a one‐dimensional zigzag chain and a two‐dimensional sheet. Poly[[bis(3,5‐di‐tert‐butylbenzene‐1,2‐diolato)bis(1,5‐di‐tert‐butyl‐4‐oxocyclohexa‐2,5‐dien‐1‐yl‐3‐olato)[μ₄‐1‐hydroxy‐1,2,4,5‐tetrakis(pyridin‐4‐yl)cyclohexane]cobalt(III)]–ethanol–water 1/7/5], {[Co₂(C₁₄H₂₀O₂)₄(C₂₆H₂₄N₄O)]·7C₂H₅OH·5H₂O}_n or {[Co₂(3,5‐dbdiox)₄(tpch)}·7EtOH·5H₂O}_n, is the second structurally characterized example of a two‐dimensional coordination polymer based on linked {Co(3,5‐dbdiox)₂} units. Variable‐temperature single‐crystal X‐ray diffraction studies suggest that catena‐poly[[[(3,5‐di‐tert‐butylbenzene‐1,2‐diolato)(1,5‐di‐tert‐butyl‐4‐oxocyclohexa‐2,5‐dien‐1‐yl‐3‐olato)cobalt(III)]‐μ‐1‐hydroxy‐1,2,4,5‐tetrakis(pyridin‐4‐yl)cyclohexane]–ethanol–water (1/1/5)], {[Co(C₁₄H₂₀O₂)₂(C₂₆H₂₄N₄O)]·C₂H₅OH·5H₂O}_n or {[Co(3,5‐dbdiox)₂(tpch)]·EtOH·5H₂O}_n, undergoes a temperature‐induced valence tautomeric interconversion.     

Ring‐opening polymerization of rac‐ and meso‐lactide initiated by indium bis(phenolate) isopropoxy complexes

Ring‐opening polymerization of rac‐ and meso‐lactide initiated by indium bis(phenolate) isopropoxides {1,4‐dithiabutanediylbis(4,6‐di‐tert‐butylphenolate)}(isopropoxy)indium ( 1 ) and {1,4‐dithiabutanediylbis(4,6‐di(2‐phenyl‐2‐propyl)phenolate)}(isopropoxy)indium ( 2 ) is found to follow first‐order kinetics for monomer conversion. Activation parameters ΔH^? and ΔS^? suggest an ordered transition state. Initiators 1 and 2 polymerize meso‐lactide faster than rac‐lactide. In general, compound 2 with the more bulky cumyl ortho‐substituents in the phenolate moiety shows higher polymerization activity than 1 with tert‐butyl substituents. meso‐Lactide is polymerized to syndiotactic poly(meso‐lactides) in THF, while polymerization of rac‐lactide in THF gives atactic poly(rac‐lactides) with solvent‐dependent preferences for heterotactic (THF) or isotactic (CH₂Cl₂) sequences. Indium bis(phenolate) compound rac‐(1,2‐cyclohexanedithio‐2,2′‐bis{4,6‐di(2‐phenyl‐2‐propyl)phenolato}(isopropoxy)indium ( 3 ) polymerizes meso‐lactide to give syndiotactic poly(meso‐lactide) with narrow molecular weight distributions and rac‐lactide in THF to give heterotactically enriched poly(rac‐lactides). © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4983–4991     

Copper(II)‐Mediated Transformation of a Tridentate Non‐Innocent Ligand into a Tetradentate Salen‐Type Innocent Ligand

A non‐innocent ligand, H₄L, was synthesized by introducing a ? CH₂NH₂ group at the ortho carbon atom to the aniline moiety of 2‐anilino‐4,6‐di‐tert‐butylphenol. The new ligand was characterized by IR and NMR spectroscopy and mass spectrometry techniques. Upon treatment with CuCl₂ ? 2 H₂O, this non‐innocent ligand provided a mononuclear four‐coordinate salen‐type Cu^II complex by complete modification of the ligand backbone. The complex was characterized by IR spectroscopy, mass spectrometry, X‐ray single‐crystal diffraction, electron paramagnetic resonance (EPR) spectroscopy, and UV/Vis/near‐IR spectroscopy techniques. X‐ray crystallographic analysis showed an asymmetric environment around the Cu^II center with a small (≈12°) twist between the two biting planes. Analysis of the X‐band EPR spectrum also supported the asymmetric environment and also indicated the presence of an unpaired electron on the d orbital. The UV/Vis/near‐IR spectrum showed strong absorption bands for metal‐to‐ligand charge transfer and ligand‐to‐metal charge transfer along with a Cu^II‐centered d–d transition. Mechanistic investigation of the formation of complex 1 indicated that modification of the ligand backbone proceeded through ligand‐centered amine to imine oxidation as well as through C? N bond‐breaking processes. During these processes, 3,5‐di‐tert‐butyl‐1,2‐benzoquinone and 2‐aminobenzylidene were produced. Ammonia, generated in situ through hydrolysis of the imine to the aldehyde, reacted with 3,5‐di‐tert‐butyl‐1,2‐benzoquinone to form the corresponding 3,5‐di‐tert‐butyl‐1,2‐iminobenzoquinone moiety, which upon two‐electron reduction in the reaction medium formed 3,5‐di‐tert‐butyl‐1,2‐aminophenol. This aminophenol underwent condensation with the H₂L5 ligand that was formed by self‐condensation of two molecules of 2‐aminobenzaldehyde and provided the modified ligand backbone.     

Attempt to Synthesize Hindered 2,4,6‐Tri‐Aryloxy‐s‐Triazines: Bis(2,4‐di‐tert‐Butylphenyl) Carbonate – Crystal Structure

Some less hindered 2,4,6‐tri‐aryloxy‐s‐triazines were synthesized through the reaction of the corresponding phenols as a starting materials with cyanogen bromide (BrCN) to obtain the corresponding arylcyanates and then trimerized. Unexpectedly, 2,4‐di‐tert‐butyl‐1‐cyanatobenzene derived from 2,4‐di‐tert‐butylphenol did not trimerize but, indeed, yielded bis(2,4‐di‐tert‐butylphenyl) carbonate. The structures of 2,4,6‐tri‐aryloxy‐s‐triazines and bis(2,4‐di‐tert‐butylphenyl) carbonate were characterized by means of IR, ¹H, and ¹³C NMR spectroscopies. Also the structure of the latter compound was studied by X‐ray crystallography.     

New Bis‐o‐Benzoquinoid Ligands with Ethylene Bridge and Their Metal Complexes

The treatment of di‐o‐quinone 4,4′‐(ethane‐1,2‐diyl)‐bis(3,6‐di‐tert‐butyl‐o‐benzoquinone) (Q–CH₂–CH₂–Q, 1 ) leads to its rearrangement to form di‐p‐quinomethide 4,4′‐(ethane‐1,2‐diylidene)bis(2‐hydroxy‐3,6‐di‐tert‐butyl‐cyclohexa‐2,5‐dienone) ( 2 ). The subsequent oxidation of 2 by an alkaline solution of K₃[Fe(CN)₆] yielded the new di‐o‐quinone 4,4′‐(ethene‐1,2‐diyl)bis(3,6‐di‐tert‐butyl‐o‐benzoquinone) (Q–CH=CH–Q, 3 ), which contains an ethylene bridge. The formation of mono‐ and poly‐reduced derivatives of 2 and 3 with potassium, thallium was studied by EPR technique. The dinuclear thallium derivative of 3 , Tl(SQ–CH=CH–SQ)Tl, was found to exist in the diamagnetic quinomethide form. The most stable derivatives of 2 and 3 are triphenyltin(IV) bis‐p‐quinomethide‐phenolate ( 4 ) and triphenylantimony(V) bis‐catecholate ( 5 ), which have been synthesized and isolated. The molecular structures of 2 , 3 , and 5 were characterized by single‐crystal X‐ray diffraction.     

Deprotonation‐Induced Aromaticity Enhancement and New Conjugated Networks in meso‐Hexakis(pentafluorophenyl)[26]hexaphyrin

meso‐Hexakis(pentafluorophenyl)‐substituted neutral hexaphyrin with a 26π‐electronic circuit can be regarded as a real homolog of porphyrin with an 18π‐electronic circuit with respect to a quite flat molecular structure and strong aromaticity. We have investigated additional aromaticity enhancement of meso‐hexakis(pentafluorophenyl)[26]hexaphyrin(1.1.1.1.1.1) by deprotonation of the inner N? H groups in the macrocyclic molecular cavity to try to induce further structural planarization. Deprotonated mono‐ and dianions of [26]hexaphyrin display sharp B‐like bands, remarkably strong fluorescence, and long‐lived singlet and triplet excited‐states, which indicate enhanced aromaticity. Structural, spectroscopic, and computational studies have revealed that deprotonation induces structural deformations, which lead to a change in the main conjugated π‐electronic circuit and cause enhanced aromaticity.     

Reactions of sterically congested 1,6‐ and 1,7‐bis(diazo)alkanes with elemental sulfur and selenium: Formation of cyclohexene, 1,2‐dithiocane, 1,2‐diselenocane,and 1,2,3‐triselenecane derivatives

The reaction of 3,8‐bis(diazo)‐2,2,4,4,7,7,9,9‐octamethyldecane ( 5 ) with elemental selenium in 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) at 130°C yielded 1,2‐di‐tert‐butyl‐3,3,6,6‐tetramethylcyclohexene ( 1 ) (64%) and trans‐3,8‐di‐tert‐butyl‐4,4,7,7‐tetramethyl‐1,2‐diselenocane ( 8 ) (13%), while that of 5 with elemental sulfur in DBU gave trans‐3, 8‐di‐tert‐butyl‐4,4,7,7‐tetramethyl‐1,2‐dithiocane ( 9 ) (77%). The reaction of 3,9‐bis(diazo)‐2,2,4,4,8,8,10,10‐octamethylundecane ( 6 ) with elemental selenium in DBU at 80°C gave a cyclic triselenide, cis‐4,10‐di‐tert‐butyl‐5,5,9,9‐tetramethyl‐1,2,3‐triselenecane ( 11 ), in 15% yield as the only identifiable product. The structures of 9 and 11 were confirmed by X‐ray crystallography. © 2002 Wiley Periodicals, Inc. Heteroatom Chem 13:351–356, 2002; Published online in Wiley Interscience (www.interscience.wiley.com). DOI 10.1002/hc.10046     

A Doubly Zwitterionic Antiaromatic [28]Hexaphyrin Formed upon Deprotonation of 5,20‐Di(N‐methyl‐4‐pyridinium)‐Substituted [28]Hexaphyrin

A rectangular 5,20‐di(4‐pyridyl) [26]hexaphyrin was reduced with NaBH₄ to give the corresponding twisted Möbius aromatic [28]hexaphyrin. Subsequent double N‐methylation gave a dicationic 5,20‐di(N‐methyl‐4‐pyridinium) [28]hexaphyrin, which was converted to a doubly zwitterionic and Hückel antiaromatic [28]hexaphyrin upon deprotonation with sodium methoxide.     

Amino‐ und halogenfunktionelle Siloxititane

Amino‐ and halofunctional Siloxititanes Amino‐di‐tert‐butylsilanol reacts with tetrabutoxititane in a molar ratio of 2:1 to give di‐n‐butoxi(bis(di‐tert‐butyl‐n‐butoxi)siloxi)titane, (C₄H₉OSi(CMe₃)₂‐O)₂Ti(OC₄H₉)₂ ( 1 ), and lithium‐di‐tert‐butylchlorosilanolate in a molar ratio of 3:1 to give n‐butoxi(tris(di‐tert‐butyl‐n‐butoxi)siloxi)titane, (H₉C₄OSi(CMe₃)₂‐O)₃TiOC₄H₉ ( 2 ). The amino‐di‐tert‐butylsilanol substitutes the four chloroatoms of TiCl₄ in the presence of triethylamine as HCl‐acceptor. The tetrakis(amino‐di‐tert‐butyl)siloxititane ( 3 ) is formed. The lithium salt of di‐tert‐butylfluorosilanol reacts with TiCl₄ in a molar ratio of 2:1 to give 1, 1, 3, 3‐tetra‐tert‐butyl‐1‐fluoro‐3‐trichlorotitoxi‐1, 3‐disiloxane, FSi(CMe₃)₂‐O‐Si(CMe₃)₂‐O‐TiCl₃ ( 4 ). In the reaction of di‐tert‐butyl‐chlorosilanol and TiCl₄, the anion [chlorosiloxi‐octa(tri‐μ²‐chlorotitanate)]^— ( 5 ) with protonated diethylether as counterion is obtained by using diethylether as HCl‐acceptor. The crystal structure determinations of 3 and 5 are reported.     

Synthese und Molekülstrukturen von N‐substituierten Diethylgallium‐2‐pyridylmethylamiden

Synthesis and Molekular Structures of N‐substituted Diethylgallium‐2‐pyridylmethylamides (2‐Pyridylmethyl)(tert‐butyldimethylsilyl)amine ( 1a ) and (2‐pyridylmethyl)‐di(tert‐butyl)silylamine ( 1b ) form with triethylgallane the corresponding red adducts 2a and 2b via an additional nitrogen‐gallium bond. These oily compounds decompose during distillation. Heating under reflux in toluene leads to the elimination of ethane and the formation of the red oils of [(2‐pyridylmethyl)(tert‐butyldimethylsilyl)amido]diethylgallane ( 3a ) and [(2‐pyridylmethyl)‐di(tert‐butyl)silylamido]diethylgallane ( 3b ). In order to investigate the thermal stability solvent‐free 3a is heated up to 400 °C. The elimination of ethane is observed again and the C‐C coupling product N, N′‐Bis(diethylgallyl)‐1, 2‐dipyridyl‐1, 2‐bis(tert‐butyldimethylsilyl)amido]ethan ( 4 ) is found in the residue. Substitution of the silyl substituents by another 2‐pyridylmethyl group and the reaction of this bis(2‐pyridylmethyl)amine with GaEt₃ yield triethylgallane‐diethylgallium‐bis(2‐pyridylmethyl)amide ( 5 ). The metalation product adds immediately another equivalent of triethylgallane regardless of the stoichiometry. The reaction of GaEt₃ with 2‐pyridylmethanol gives quantitatively colorless 2‐pyridylmethanolato diethylgallane ( 6 ).     

Homo‐ and Heteronuclear meso,meso‐(E)‐Ethene‐1,2‐diyl‐Linked Diporphyrins: Preparation,X‐ray Crystal Structure,Electronic Absorption and Emission Spectra and Density Functional Theory Calculations

Homo‐ and heteronuclear meso,meso‐(E)‐ethene‐1,2‐diyl‐linked diporphyrins have been prepared by the Suzuki coupling of porphyrinylboronates and iodovinylporphyrins. Combinations comprising 5,10,15‐triphenylporphyrin (TriPP) on both ends of the ethene‐1,2‐diyl bridge M₂10 (M₂=H₂/Ni, Ni₂, Ni/Zn, H₄, H₂Zn, Zn₂) and 5,15‐bis(3,5‐di‐tert‐butylphenyl)porphyrinato‐nickel(II) on one end and H₂, Ni, and ZnTriPP on the other ( M₂11 ), enable the first studies of this class of compounds possessing intrinsic polarity. The compounds were characterized by electronic absorption and steady state emission spectra, ¹H NMR spectra, and for the Ni₂ bis(TriPP) complex Ni₂10 , single crystal X‐ray structure determination. The crystal structure shows ruffled distortions of the porphyrin rings, typical of Ni^II porphyrins, and the (E)‐C₂H₂ bridge makes a dihedral angle of 50° with the mean planes of the macrocycles. The result is a stepped parallel arrangement of the porphyrin rings. The dihedral angles in the solid state reflect the interplay of steric and electronic effects of the bridge on interporphyrin communication. The emission spectra in particular, suggest energy transfer across the bridge is fast in conformations in which the bridge is nearly coplanar with the rings. Comparisons of the fluorescence behaviour of H₄10 and H₂Ni10 show strong quenching of the free base fluorescence when the complex is excited at the lower energy component of the Soret band, a feature associated in the literature with more planar conformations. TDDFT calculations on the gas‐phase optimized geometry of Ni₂10 reproduce the features of the experimental electronic absorption spectrum within 0.1 eV.     

Novel Dinuclear Redox‐isomeric Complexes with a Tetrapodal Pyridine‐based Ligand

Tris‐o‐semiquinonato cobalt complexes react with a tetrapodal pyridine‐derived ligand to form dinuclear cobalt compounds of general formula (OMP)[CoQ₂]₂, where OMP = 2,2′‐(pyridine‐2,6‐diyl)bis(N¹,N¹,N³,N³‐tetramethylpropane‐1,3‐diamine), Q = mono‐ or dianion of 3,6‐di‐tert‐butyl‐o‐benzoquinone (complex 1 ) and it derivatives: 3,6‐di‐tert‐butyl‐4,5‐N,N′‐piperazino‐o‐benzoquinone (complex 2 ), and 3,6‐di‐tert‐butyl‐4‐Cl‐o‐benzoquinone (complex 3 ). Single crystal X‐ray crystallography of 1 and 3 indicates two bis‐quinonato cobalt units bound by an OMP ligand, which acts as a bridge. Each central cobalt atom is chelated by one N¹,N¹,N³,N³‐tetramethylpropane‐1,3‐diamine and two o‐quinonato fragments. The nitrogen atom of the pyridine ring is uncoordinated. All complexes were characterized by NIR‐IR and EPR spectroscopy, precise adiabatic vacuum calorimetry, and by variable‐temperature magnetic susceptibility measurements. All data indicate a reversible thermally driven redox‐isomeric (valence tautomeric) transformation in the solid state for all complexes.     

Synthesis of ultra‐low‐molecular‐weight polyethylene wax using a bulky Ti(IV) aryloxide–alkyl aluminum catalytic system

Complexes of titanium(IV) with bulky phenolic ligands such as 2‐tert‐butyl‐4 methylphenol, 2, 4‐di‐tert‐butyl phenol and 3,5‐di‐tert‐butyl phenol were prepared and characterized. These catalyst precursors, formulated as [Ti(OPh*)_n(OPrⁱ)_4?n] (OPh* = substituted phenol), were found to be active in polymerization of ethylene at higher temperatures in combination with ethylaluminum sesquichloride (Et₃Al₂Cl₃) as co‐catalyst. It was observed that the reaction temperature and ethylene pressure had a pronounced effect on polymerization and the molecular weight of polyethylene obtained. In addition, this catalytic system predominantly produced linear, crystalline ultra‐low‐molecular‐weight polyethylenes narrow dispersities. The polyethylene waxes obtained with this catalytic system exhibit unique properties that have potential applications in surface coating and adhesive formulations. Copyright © 2007 John Wiley & Sons, Ltd.     

Pyrene‐Bridged Boron Subphthalocyanine Dimers: Combination of Planar and Bowl‐Shaped π‐Conjugated Systems for Creating Uniquely Curved π‐Conjugated Systems

Pyrene‐bridged boron subphthalocyanine dimers were synthesized from a mixed‐condensation reaction of 2,7‐di‐tert‐butyl‐4,5,9,10‐tetracyanopyrene and tetrafluorophthalonitrile, and their syn and anti isomers arising from the result of connecting two bowl‐shaped boron subphthalocyanine molecules were successfully separated. Expansion of the conjugated system of boron subphthalocyanine through a pyrene bridge caused a redshift of the Q band absorption relative to the parent pyrene‐fused monomer, whereas combining the curved π‐conjugation of boron subphthalocyanine with the planar π‐conjugation of pyrene enabled facile embracement of C₆₀ molecules, owing to the enhanced concave–convex π–π stacking interactions.