Boron Difluoride Complexes of Expanded N‐Confused Calix[<i>n</i>]phyrins That Demonstrate Unique Luminescent and Lasing Properties

Ishida, Masatoshi; Omagari, Toshihiro; Hirosawa, Ryuji; Jono, Keisuke; Sung, Young Mo; Yasutake, Yuhsuke; Uno, Hidemitsu; Toganoh, Motoki; Nakanotani, Hajime; Fukatsu, S.; Kim, Dongho; Furuta, Hiroyuki

doi:10.1002/anie.201606246

Cited by 46 publications

(32 citation statements)

References 52 publications

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“…BODIPYs have been used for many applications such as optical materials, solar cells, biological imaging, and sensitizers for photodynamic therapy [5][6][7]. Among BODIPY derivatives, cyclic BODIPY oligomers show distinct electronic and optical properties such as unique luminescent and lasing properties, cation recognition, and switchable near infrared (NIR) responses [8][9][10][11][12][13][14][15]. Shinokubo and co-workers developed the synthesis of planar BODIPY dimer and trimer (c-BODIPY-1), linked through butadiyne by sila-Glaser coupling reaction ( Figure 1) [9].…”

Section: Introductionmentioning

confidence: 99%

“…Their results show that the expanded porphyrins containing π-conjugated bridging units could be excellent precursors for the preparation of cyclic BODIPY oligomers. However, research on cyclic BODIPY oligomers is still limited due to few efficient synthesis methods [8][9][10][11][12][13][14][15]. Moreover, the relationship between the number of coordinated boron atoms and molecular configuration/optical properties of expanded porphyrins is still unclear.…”

Section: Introductionmentioning

confidence: 99%

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Vinylene-Bridged Cyclic Dipyrrin and BODIPY Trimers

Xue

Kuzuhara

Aratani

et al. 2020

IJMS

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Vinylene-bridged cyclic boron–difluoride complex of dipyrrin (BODIPY) trimers were successfully prepared from expanded dimethyl-vinylene bridged hexaphyrin(2.1.2.1.2.1) Me-Hex that has the structure of alternate dipyrrins and vinylene bridges. The hexaphyrin(2.1.2.1.2.1) Me-Hex can coordinate with boron ions to afford five kinds of cyclic BODIPYs given by step-by-step boron complexations. Crystal structures of all cyclic BODIPYs except for 3BF2-Me-Hex(b) formed non-planar structures. The theoretical calculation predicted that mono-/bis-boron cyclic BODIPYs show the intramolecular charge transfer (ICT) characteristics, whereas tri-boron cyclic BODIPYs have no ICT characteristics. Reflecting these electronic properties, tri-boron cyclic BODIPYs exhibit weak fluorescence in the red region, but mono-/bis-boron cyclic BODIPYs exhibit no emission. Vinylene bridged cyclic dipyrrin trimer Me-Hex is the novel porphyrinoid ligand allowed to control the boron coordination under different reaction conditions to form various boron complexes.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Vinylene-Bridged Cyclic Dipyrrin and BODIPY Trimers

Xue

Kuzuhara

Aratani

et al. 2020

IJMS

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“…In addition, the ROESY spectrum revealed the distinct cross peaks originated from the proximity of the specific regular pyrrole NH and β‐pyrrolic CH (Figure S6). Based on these observations, we proposed that transformation to a dumbbell‐shaped core structure (i.e., 2 b ) with alternately twisted dipyrrin units through flipping out the confused pyrrole rings of 2 a . At the equilibrium (after 24 h), the final ratio of 2 a and 2 b was estimated to be 5:1 at 298 K, indicating the Gibbs free energy difference of ca.…”

Section: Methodsmentioning

confidence: 99%

Doubly N‐Confused [36]Octaphyrin(1.1.1.1.1.1.1.1): Isomerization, Bis‐Metal Coordination, and Topological Chirality

et al. 2017

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A novel [36]octaphyrin analogue embedding two N-confused pyrrole units demonstrated unique prototropy-coupled isomerization between the Figure-of-eight and dumbbell conformers. Upon bis-metal coordination, fixation of fully π-conjugated Figure-of-eight structures was achieved as referred from the X-ray crystal structure. Chirogenesis of the helical enantiomers was proved by intense circular dichroism (CD) response in the near infrared (NIR) region.

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“…Various macrocycles with unique properties were synthesized by altering the linking unit between the BODIPY nuclei and by changing the number of repeating units. [56][57][58][59][60][61][62][63][64][65] In particular, Nabeshima and coworkers focused on the unique shapes and the molecular recognition properties of the cyclic BODIPY oligomers. As already mentioned, the fluorine atoms of the BF 2 unit are negatively charged, and they can interact with a cationic molecule such as ammonium ions.…”

Section: Scheme 2 Synthesis Of Selenophenyl Bodipy Oligomers 3 Cyclicmentioning

confidence: 99%

Synthesis and Functions of Oligomeric and Multidentate Dipyrrin Derivatives and their Complexes

Chiba¹,

Nakamura²,

Matsuoka³

et al. 2020

Synlett

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The dipyrrin–metal complexes and especially the boron complex 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) have recently attracted considerable attention because of their interesting properties and possible applications. We have developed two unique and useful ways to extend versatility and usefulness of the dipyrrin complexes. The first one is the linear and macrocyclic oligomerization of the BODIPY units. These arrangements of the B–F moieties of the oligomerized BODIPY units provide sophisticated functions, such as unique recognition ability toward cationic guest, associated with changes in the photophysical properties by utilizing unprecedented interactions between the B–F and a cationic species. The second one is introduction of additional ligating moieties into the dipyrrin skeleton. The multidentate N2Ox dipyrrin ligands thus obtained form a variety of complexes with 13 and 14 group elements, which are difficult to synthesize using the original N2 dipyrrin derivatives. Interestingly, these unique complexes exhibit novel structures, properties, and functions such as guest recognition, stimuli-responsive structural conversion, switching of the optical properties, excellent stability of the neutral radicals, etc. We believe that these multifunctional dipyrrin complexes will advance the basic chemistry of the dipyrrin complexes and develop their applications in the materials and medicinal chemistry fields.1 Introduction2 Linear Oligomers of Boron–Dipyrrin Complexes3 Cyclic Oligomers of Boron–Dipyrrin Complexes4 A Cyclic Oligomer of Zinc–Dipyrrin Complexes5 Group 13 Element Complexes of N2Ox Dipyrrins6 Chiral N2 and N2Ox Dipyrrin Complexes7 Group 14 Element Complexes of N2O2 Dipyrrins8 Other N2O2 Dipyrrin Complexes with Unique Properties and Functions9 Conclusion

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Boron Difluoride Complexes of Expanded N‐Confused Calix[n]phyrins That Demonstrate Unique Luminescent and Lasing Properties

Cited by 46 publications

References 52 publications

Vinylene-Bridged Cyclic Dipyrrin and BODIPY Trimers

Vinylene-Bridged Cyclic Dipyrrin and BODIPY Trimers

Doubly N‐Confused [36]Octaphyrin(1.1.1.1.1.1.1.1): Isomerization, Bis‐Metal Coordination, and Topological Chirality

Synthesis and Functions of Oligomeric and Multidentate Dipyrrin Derivatives and their Complexes

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