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Synthesis of tetraarylethene luminogens by C−H vinylation of aromatic compounds with triazenes

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Academic year: 2021

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Safety note: As many other azides, phenyl azide poses a risk of explosion, so a protective blast shield is recommended during the synthesis and purification. In the syntheses described below, PhN3 was prepared following a literature procedure1 and used undistilled.





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Compound TPEǦTr MeǦTPEǦTr 17 18 21

‘”—Žƒ ʹ͸ ʹͳ͵ ʹͻ ʹ͹͵ ʹͻ ʹͷ” ʹͶ ͳͺ ʹͷ ʹͳ Dcalc.Ȁ‰…Ǧ͵ ͳǤʹͷʹ ͳǤʹͳͶ ͳǤ͵ʹͻ ͳǤʹͶͻ ͳǤͳͻͲ PȀǦͳ ͲǤͷ͹͸ ͲǤͷͷͲ ʹǤͷͶ͸ ͲǤͷ͹͹ ͲǤͷʹͲ ‘”—Žƒ‡‹‰Š– ͵͹ͷǤͶ͸ Ͷͳ͹Ǥͷ͵ Ͷͷ͵ǤͶͲ ͵ʹʹǤ͵ͺ ͵͵ͷǤͶ͵ ‘Ž‘—” ›‡ŽŽ‘™ ›‡ŽŽ‘™ …Ž‡ƒ”…‘Ž‘—”Ž‡•• …Ž‡ƒ”’ƒŽ‡‰”‡‡ …Ž‡ƒ”…‘Ž‘—”Ž‡•• Šƒ’‡ ’”‹• ’”‹• ’”‹• ’”‹• ’”‹• ‹œ‡Ȁ͵ ͲǤͳʹͳšͲǤͲͻͺš ͲǤͲͻͳ ͲǤͷͻ͹šͲǤͷʹ͹š ͲǤʹ͹Ͷ ͲǤʹ͹έͲǤʹͳέͲǤͳ͵ ͲǤͶͶέͲǤʹ͹έͲǤʹͲ ͲǤͶ͸έͲǤͶͲέͲǤʹͷ TȀ ͳͶͲǤͲͲȋͳͲȌ ͳͶͲǤͲͲȋͳͲȌ ͳͶͲǤͲͳȋͳͲȌ ͳͶͲǤͲͲȋͳͲȌ ͳͲͲǤͲͲȋͳͲȌ ”›•–ƒŽ›•–‡ –”‹…Ž‹‹… ”‹…Ž‹‹… ‘”–Š‘”Š‘„‹… –”‹…Ž‹‹… ‘‘…Ž‹‹… ’ƒ…‡”‘—’ P P ͳʹͳʹͳ P  ͳ aȀ% ͻǤͳͶ͵ͷȋ͹Ȍ ͻǤͳ͹ͷͺȋ͸Ȍ ͻǤ͵ͻͷ͵ȋʹȌ ͺǤͶͻͲͳȋ͹Ȍ ͻǤͺ͵ͶͺȋͺȌ bȀ% ͻǤͺͳͶͳȋͺȌ ͳͲǤͷͳͷͺȋͷȌ ͳ͵Ǥ͸ͻͺͳȋ͵Ȍ ͻǤͶ͸ͳͶȋ͹Ȍ ͻǤͶͻ͹ʹȋͷȌ cȀ% ͳʹǤ͵Ͷ͵ͲȋͳͳȌ ͳʹǤͺͷͺͺȋͻȌ ͳ͹Ǥ͸ͲͷʹȋͶȌ ͳͳǤͳͶ͵ͺȋͻȌ ͳͲǤͶͲͺʹȋ͹Ȍ DȀι ͸ͺǤͳͻͺȋͺȌǤ ͺʹǤͻʹͲȋͷȌǤ ͻͲ ͹ͷǤͻͶͶȋ͹Ȍ ͻͲ EȀι ͺͲǤͳͶʹȋ͹Ȍ ͸ͻǤͻ͵͸ȋ͸Ȍ ͻͲ ͺ͹Ǥͳ͸ͻȋ͸Ȍ ͳͲͷǤ͹ͲͲȋͺȌ JȀι ͹͸Ǥ͸͹͵ȋ͹Ȍ ͹ͻǤʹͳͻȋͶȌ ͻͲ ͺͲǤͺ͹Ͷȋ͹Ȍ ͻͲ Ȁ%͵ ͻͻ͸Ǥͳͺȋͳ͸Ȍ ͳͳͶʹǤͷͶȋͳ͵Ȍ ʹʹ͸ͷǤ͹ͷȋͻȌ ͺͷ͹Ǥ͵ͳȋͳʹȌ ͻ͵ͷǤͺͻȋͳͳȌ Z ʹ ʹ Ͷ ʹ ʹ Z' ͳ ͳ ͳ ͳ ͳ ƒ˜‡Ž‡‰–ŠȀ% ͳǤͷͶͳͺͶ ͳǤͷͶͳͺͶ ͳǤͷͶͳͺͶ ͳǤͷͶͳͺͶ ͳǤͷͶͳͺͶ ƒ†‹ƒ–‹‘–›’‡ —KD —KD —KD —KD —KD 4minȀι ͵Ǥͺ͹ͷ ͵Ǥ͸͸͹ ͷǤͲʹͶ ͶǤͲͻͲ ͶǤ͸͹Ͳ 4maxȀι ͹ͷǤʹʹ͹ ͹ͷǤʹͶͺ ͹͵Ǥͷ͸Ͷ ͹͵Ǥ͹ͷʹ ͹ͶǤ͸ʹͻ ‡ƒ•—”‡†‡ˆŽǤ ͸ͺͶͶ Ͷ͹Ͳͻ ͳͷ͵ʹʹ ͵ͶͶͻ ͳͶͳ͸Ͳ †‡’‡†‡–‡ˆŽǤ ͵ͻ͹Ͳ Ͷ͹Ͳͻ ͶͶͺͷ ͵ͶͶͻ ͵͹ʹ͹ ‡ˆŽ‡…–‹‘•™‹–Š εʹȋ Ȍ ͵ͳͻ͵ ͵ͺͻ͸ Ͷʹͻͷ ʹ͹ͺͳ ͵ͶͲͻ Rint ͲǤͲͳͻͳ Ȁƒ ͲǤͲ͵͵͸ Ȁƒ ͲǤͲ͵ʹ͹ ƒ”ƒ‡–‡”• ͵ͷͲ ͵ͺͻ ͵ͶͶ ʹ͵Ͷ ͵Ͳ͵ ‡•–”ƒ‹–• ͳ Ͳ ͵͵Ͳ Ͳ Ͷ͸Ͳ ƒ”‰‡•–‡ƒȀ‡%Ǧ͵ ͲǤʹͳͳ ͲǤʹͲ͹ ͲǤͶͲͳ ͲǤ͵ͷͺ ͲǤʹͷ͹ ‡‡’‡•– ‘Ž‡Ȁ‡%Ǧ͵ ǦͲǤʹͲ͸ ǦͲǤʹ͸͹ ǦͲǤ͹ͶͶ ǦͲǤʹͳʹ ǦͲǤ͵ͲͲ ‘‘  ͳǤͲͳͳ ͳǤͲ͵ͳ ͳǤͲ͹ͳ ͳǤͲͷʹ ͳǤͲͷͻ wR2ȋƒŽŽ†ƒ–ƒȌ ͲǤͳͲʹͳ ͲǤͳ͵ͳͺ ͲǤͳ͸ͻͳ ͲǤʹͲ͵ͺ ͲǤʹ͵͸ʹ wR2 ͲǤͲͻ͵ͺ ͲǤͳʹͷͲ ͲǤͳ͸͸͸ ͲǤͳͻ͸͵ ͲǤʹ͵ͲͶ R1ȋƒŽŽ†ƒ–ƒȌ ͲǤͲͶͻͺ ͲǤͲͷ͵ͺ ͲǤͲͷ͹ʹ ͲǤͲ͹͸ͻ ͲǤͲ͹ͺʹ R1 ͲǤͲ͵͹Ͷ ͲǤͲͶͶ͹ ͲǤͲͷͷͶ ͲǤͲ͸͸ͻ ͲǤͲ͹ͷ͵ …‘†‡ ͳͻ͵ͺ͸ͳͺ ͳͻ͵ͺ͸ͳͻ ͳͻ͵ͺ͸ʹʹ ͳͻ͵ͺ͸ʹͳ ͳͻ͵ͺ͸ʹͲ

(36)

^ϯϲ 105VSHFWUD  +105 0+]&'&O VSHFWUXPRI73(7U  &105 0+]&'&O VSHFWUXPRI73(7U

(37)

^ϯϳ                               +105 0+] &' 62 VSHFWUXPRI73(7U                        &105 0+] &'  62 VSHFWUXPRI73(7U 

(38)

^ϯϴ  ,5 ILOP VSHFWUXPRI73(7U                         FP 7 FP FP FP FP FP FP FP FP FP FP FP FP FP FP FP FP FP FP FP FP FP FP FP FP FP FP FP FP FP

(39)

^ϯϵ        SSP                           +105 0+]&'&O VSHFWUXPRI0H73(7U                       &105 0+]&'&O  VSHFWUXPRI0H73(7U 

(40)

^ϰϬ        SSP                                                                                  

+105 0+]&'&O VSHFWUXPRI&O73(7U(* peaks of pentane and Et2O)

             SSP                                                                           &105 0+]&'&O

 VSHFWUXPRI&O73(7U(* peaks of pentane and Et2O)

 Ύ Ύ Ύ Ύ Ύ Ύ Ύ Ύ

(41)

^ϰϭ  +105 0+]&'&O  VSHFWUXPRI)73(7U                       &105 0+]&'&O VSHFWUXPRI)73(7U 

(42)

^ϰϮ   +105 0+]&'&O VSHFWUXPRI  &105 0+]&'&O  VSHFWUXPRI

(43)

^ϰϯ  +105 0+]&'&O  VSHFWUXPRI              SSP                                        &105 0+]&'&O  VSHFWUXPRI 

(44)

^ϰϰ          SSP                 +105 0+]&'&O VSHFWUXPRI          SSP                   &105 0+]&'&O  VSHFWUXPRI 

(45)

^ϰϱ                      +105 0+]&'&O  VSHFWUXPRI  &105 0+]&'&O  VSHFWUXPRI 

(46)

^ϰϲ  +105 0+]&'&O VSHFWUXPRI       SSP      )105 0+]&'&O  VSHFWUXPRI 

(47)

^ϰϳ          SSP                   &105 0+]&'&O VSHFWUXPRI  

(48)

^ϰϴ         SSP                            +105 0+]&'&O VSHFWUXPRI              SSP                       &105 0+]&'&O  VSHFWUXPRI 

(49)

^ϰϵ          SSP                     +105 0+]&'&O VSHFWUXPRI              SSP                       &105 0+]&'&O  VSHFWUXPRI 

(50)

^ϱϬ         SSP                        +105 0+]&'&O VSHFWUXPRI  &105 0+]&'&O  VSHFWUXPRI 

(51)

^ϱϭ         SSP                         +105 0+]&'&O VSHFWUXPRI  &105 0+]&'&O  VSHFWUXPRI 

(52)

^ϱϮ                 +105 0+]&'&O  VSHFWUXPRI              SSP                                           &105 0+]&'&O  VSHFWUXPRI 

(53)

^ϱϯ          SSP                     +105 0+]&'&O VSHFWUXPRI                        &105 0+]&'&O  VSHFWUXPRI 

(54)

^ϱϰ         SSP                               +105 0+]&'&O VSHFWUXPRI                           &105 0+]&'&O  VSHFWUXPRI 

(55)

^ϱϱ          SSP                              +105 0+]&'&O VSHFWUXPRI              SSP                         &105 0+]&'&O  VSHFWUXPRI 

(56)

^ϱϲ        SSP                        +105 0+]&'&O VSHFWUXPRI                            &105 0+]&'&O  VSHFWUXPRI 

(57)

^ϱϳ                       +105 0+]&'&O  VSHFWUXPRI                         &105 0+]&'&O VSHFWUXPRI 

(58)

^ϱϴ          SSP                        +105 0+]&'&O VSHFWUXPRI                 &105 0+]&'&O  VSHFWUXPRI 

(59)

^ϱϵ  +105 0+]&'&O VSHFWUXPRI              SSP                       &105 0+]&'&O  VSHFWUXPRI 

(60)

^ϲϬ         SSP                  +105 0+]&'&O VSHFWUXPRI                         &105 0+]&'&O  VSHFWUXPRI 

(61)

^ϲϭ          SSP                                  +105 0+]&'&O VSHFWUXPRI              SSP                       &105 0+]&'&O  VSHFWUXPRI 

(62)

^ϲϮ  +105 0+]&'&O VSHFWUXPRI                   &105 0+]&'&O  VSHFWUXPRI 

(63)

^ϲϯ                                     +105 0+]&'&O  VSHFWUXPRI                           &105 0+]&'&O VSHFWUXPRI 

(64)

^ϲϰ  +105 0+]&'&O VSHFWUXPRI                   &105 0+]&'&O  VSHFWUXPRI 

(65)

^ϲϱ                SSP                            +105 0+]&'&O VSHFWUXPRI              SSP                       &105 0+]&'&O  VSHFWUXPRI

(66)

^ϲϲ                SSP                             +105 0+]&'&O VSHFWUXPRI              SSP                      &105 0+]&'&O  VSHFWUXPRI 

(67)

^ϲϳ  +105 0+]&'&O VSHFWUXPRI              SSP                               &105 0+]&'&O  VSHFWUXPRI 

(68)

^ϲϴ  +105 0+]&'&O VSHFWUXPRI  &105 0+]&'&O VSHFWUXPRI 

(69)

^ϲϵ                       +105 0+]&'&O  VSHFWUXPRI                            &105 0+]&'&O VSHFWUXPRI 

(70)

^ϳϬ                SSP                           

+105 0+]&'&O VSHFWUXPRI



&105 0+]&'

&O VSHFWUXPRI

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