Synthèse et valorisation de ligands dipyrrométhène bis-triazole
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(2) N°d’ordre NNT : 2016LYSE1254. THESE de DOCTORAT DE L’UNIVERSITE DE LYON opérée au sein de. l’Université Claude Bernard Lyon 1 Ecole Doctorale N° 206 Chimie, Procédés, Environnement Spécialité de doctorat : Chimie Discipline : Chimie organique. Soutenue publiquement le 24/11/2016, par :. Charles Guérin. Synthèse et valorisation de ligands dipyrrométhène bis-triazole. Devant le jury composé de : Andraud, Chantal. Directrice de Recherche CNRS, ENS Lyon. Examinatrice. Baudron, Stéphane Chargé de Recheche CNRS, Univ. Strasbourg Siri, Olivier Directeur de Recherche CNRS, Univ. Marseille Py, Sandrine Chargée de Recherche CNRS, Univ. Grenoble. Rapporteur Rapporteur Examinatrice. Andrioletti, Bruno Gérard, Ludivine. Directeur de thèse Co-directrice de thèse. . Professeur, Univ. Lyon 1 Chargée de Recherche CNRS, Univ. Lyon 1. .
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(4) UNIVERSITE CLAUDE BERNARD - LYON 1 Président de l’Université. M. le Professeur Frédéric FLEURY. Président du Conseil Académique. M. le Professeur Hamda BEN HADID. Vice-président du Conseil d’Administration. M. le Professeur Didier REVEL. Vice-président du Conseil Formation et Vie Universitaire. M. le Professeur Philippe CHEVALIER. Vice-président de la Commission Recherche. M. Fabrice VALLÉE. Directrice Générale des Services. Mme Dominique MARCHAND. COMPOSANTES SANTE Faculté de Médecine Lyon Est – Claude Bernard. Directeur : M. le Professeur G. RODE. Faculté de Médecine et de Maïeutique Lyon Sud – Charles Directeur : Mme la Professeure C. BURILLON Mérieux Directeur : M. le Professeur D. BOURGEOIS. Faculté d’Odontologie Institut des Sciences Pharmaceutiques et Biologiques Institut des Sciences et Techniques de la Réadaptation Département de formation et Centre de Recherche en Biologie Humaine. Directeur : Mme la Professeure C. VINCIGUERRA Directeur : M. X. PERROT Directeur : Mme la Professeure A-M. SCHOTT. COMPOSANTES ET DEPARTEMENTS DE SCIENCES ET TECHNOLOGIE Faculté des Sciences et Technologies. Directeur : M. F. DE MARCHI. Département Biologie. Directeur : M. le Professeur F. THEVENARD. Département Chimie Biochimie. Directeur : Mme C. FELIX. Département GEP. Directeur : M. Hassan HAMMOURI. Département Informatique. Directeur : M. le Professeur S. AKKOUCHE. Département Mathématiques. Directeur : M. le Professeur G. TOMANOV. Département Mécanique. Directeur : M. le Professeur H. BEN HADID. Département Physique. Directeur : M. le Professeur J-C PLENET. UFR Sciences et Techniques des Activités Physiques et Sportives Directeur : M. Y. VANPOULLE Observatoire des Sciences de l’Univers de Lyon. Directeur : M. B. GUIDERDONI. Polytech Lyon. Directeur : M. le Professeur E. PERRIN. Ecole Supérieure de Chimie Physique Electronique. Directeur : M. G. PIGNAULT. Institut Universitaire de Technologie de Lyon 1. Directeur : M. le Professeur C. VITON. Ecole Supérieure du Professorat et de l’Education. Directeur : M. le Professeur A. MOUGNIOTTE. Institut de Science Financière et d'Assurances . Directeur : M. N. LEBOISNE. . .
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(20) "=I 4I(3-H -= j ;I I@=J (@<F@I/I ,- ,-KQ FRHH@;-I ;4/I F"H K= F@=J </J3.=-g "KJ@H4I"=J ;" (@=9K2"4I@= /;-(JH@=4GK- -=JH- ;-I ,-KQ 3/J/H@(R(;-Ij " =K</H@J"J4@= IRIJ/<"J4GK- s t K H"FF-;/- IKH ;" 42KH- -IJ F-K -<F;@R/- F@KH ,/(H4H- ;-I ,411/H-=J-I F@I4J4@=I,-IIj"=@<-=(;"JKH-KIK-;;-L-IJFH/1/H/-gKJ4;4I"=J;-IJ-H<-I,-F@I4J4@=Iα@Kβo FRHH@;4GK-I"4=I4GK-,-F@I4J4@=/$72I4JK/-IKH;-F@=J</J3.=-g,4J"KII4l</J34=-mj -IIF-KO-=J0JH-(@=I4,/H/I(@<<-,-I,-<4oF@HF3RH4=-Ig,@=J;"IJHK(JKH-;"F;KII4<F;--IJ ;" F@HF34=- Mj " =/(-II4J/ ,- ,/O-;@FF-H ;" IR=J3.I- ,- F@HF3RH4=-I F-K @K F"I IR</JH4GK-I " "K2<-=J/ ;k"JJH"4J ,-I I(4-=J414GK-I F@KH ;-I Ig =@J"<<-=J 2H%(- # ;-KH ("F"(4J/ # (H4IJ";;4I-Hg 1"(4;4J"=J(@=I4,/H"';-<-=J;-I/J"F-I,-FKH414("J4@=j méso 3 2. 5. 4. NH 1. 10. 6. 7 8. N 11. β. 9. β. NH. N. β NH. α. β. N. N. HN. α. 1. 2. 3. . )'96"WH2/"0 . 896" "8979".."!"7!)4=662/$8(#0"7E"8 2/4 6 )720 :" . 4264()0". -,4FRHH@</J3.=-KJ@J";-<-=J=@=oIK'IJ4JK/FH/I-=J-K=-JH.I2H"=,-4=IJ"'4;4J/j ;I-,/2H",--= I@;KJ4@=#,-IJ-<F/H"JKH-IIKF/H4-KH-I#o ~jk"'I-=(-,-IK'IJ4JKJ4@=;-H-=,JH.IOK;=/H"';- "KQ "JJ"GK-I /;-(JH@F34;-I -J =K(;/@F34;-Ij - ,/O-;@FF-<-=J ,- J-(3=4GK-I IR=J3/J4GK-I F-H<-JJ"=J ,- IK'IJ4JK-H ;-I F@I4J4@=I αg β -J /$72 @=J F-H<4I ,k"((/,-H # ,-I I IJ"';-I -J 4I@;"';-Ij . . .
(21) j 4I(3-Hg
(22) jHJ3g)"("/)"!"7=662.7g:",-<4I(3- -H;"2jKSMQgO@;jj j j @@,gj3@<FI@=g("/H":HLJJQgWV]gj jj-JS:-Hg "J-=J nngLJJMj . .
(23) 6,2&"1! !1 '.600-+#2&",!1 - <"=4.H- 2/=/H";-g ;-I ,4FRHH@</J3.=-I I@=J IR=J3/J4I/I F"H (@=,-=I"J4@= ,- ,-KQ ,/H4O/I FRHH@;4GK-IIKHK=,/H4O/("H'@=R;/g1@H<"=J;-F@=J/$72F-=,"=J;"H/"(J4@=j-I,411/H-=J-IO@4-I ,k"((.I"KQI@=J/J/H/IK</-IF"HHN(:=-H"8 .H -IIIR</JH4GK-IF-KO-=J0JH-@'J-=KIs(3/<"tF"H(@=,-=I"J4@=,-,-KQ/GK4O";-=JI,kK= FRHH@;- N IKH K= 3";@2/=KH- ,k"(4,- F-H<-JJ"=J ,k"((/,-H # K= ,4FRHH@</J3.=- IR</JH4GK- </I@o IK'IJ4JK/OgFH@J@==/#("KI-,-I(@=,4J4@=I"(4,-Ij"=I(-("Ig;-FRHH@;-,@4JF@II/,-HK=-,-I-I ,-KQF@I4J4@=Iα ;4'H-F@KHF-H<-JJH-;k"JJ"GK-=K(;/@F34;-IKH;-,/H4O/("H'@=R;/j O R2 2. R3. R1. R3. N H 4. R1. R3. NH N HCl. R2 R1. 5 R3. R3 N H 6. R4. Cl R2. R1. R2 2. R4. HCOOH. CO2Et. R2. R3 NH. R2. N. R1. R1 7. . ($/ WH=08(#7"!I907=/$86)59". ";4'/H"J4@=,-;"F@I4J4@=αF-KJ"KII4I-1"4H-)07)89F"H,/("H'@QR;"J4@=,kK=FRHH@;R;o-IJ-HPF"H ;k"(4,-1@H<4GK-j ;9@K-/2";-<-=J;-HB;-,-IR=J3@=("H'@=R;-,@=="=J"((.I"KIR</JH4GK- Q=@=oIK'IJ4JK/-=F@I4J4@=/$72j k"((.I"KQI,4IIR</JH4GK-Is(3/<"t=/(-II4J-;"FH/o1@=(J4@==";4I"J4@=,kK=FRHH@;-F"HK= 2H@KF-<-=J("H'@=R;/j"FH/I-=(-,kK=";,/3R,-R-=F@I4J4@=αF-H<-J"FH.I"JJ"GK-,kK="KJH- FRHH@;- F"H ("J";RI- "(4,- ,k@'J-=4H ;- ,4FRHH@</J3.=- ,4IIR</JH4GK- S =@=oIK'IJ4JK/ -= F@I4J4@= /$72j"=I;-("I,kK=-FH/o1@=(J4@==";4I"J4@=F"HK=-(/J@=-KJg;"(@=,-=I"J4@="O-(;-FRHH@;--IJ "(J4O/-F"H;F@KH(@=,K4H-"K,4IIR</JH4GK-/$72IK'IJ4JK/KKj . . jHN(:=-Hg j"HK="H"J=-gjj-JJ42gj@;F34=g 0H
(24) H("/HKSSPg]Zgj j Kgj4"@g j"=gj "=2g j Kg j Kg j "=2g!j "=2g j
(25) "@g0'";H("/H 08H!HLJKLg[Wgj. .
(26) R2. R3. R4. R3. R5 HBr. O R1. N H 8. N H. R2 R1. R3. R4. N H 10. R2. R6. R7. R7. R3 POCl3. N H. NH N HBr 9. R1. R5. O. R4. R2. R6. NH R1. 11. R5 R6 R4 R5. N R6. . ($/ XH=08(#7"!"7!)77=/$86)59"7. "=I ;-I ("I FH/I-=J/I (4o,-IIKIg ;" (@=,-=I"J4@= (@=,K4J ,4H-(J-<-=J # ;" 1@H<"J4@= ,K ,4FRHH@</J3.=-s1@H<-@QR,/-tg,"=I;-GK-;;-I,-KQFRHH@;-II@=J(@=9K2K/Ij"(@=,-=I"J4@=F-KJ /2";-<-=J ,@==-H K= 4=J-H</,4"4H- =@=o(@=9K2K/g "FF-;/ ,4FRHH@</J3"=-j ;I @=J F@KH ("H"(J/H4IJ4GK- ,k"O@4H "K <@4=I K= "J@<- ,k3R,H@2.=- -= F@I4J4@= /$72j 4=,I-R "8 2..H @=J F"HJ4(K;4.H-<-=J JH"O"4;;/ # ;" IR=J3.I- ,- (-I 4=J-H</,4"4H-Ig FH/(KHI-KHI ,- F@HF3RH4=-Ij " (@=,-=I"J4@= ,K FRHH@;- IKH ,-I ,/H4O/I ,K '-=S";,/3R,- s(3/<" t F-H<-J ,k@'J-=4H ,-I ,4FRHH@</J3"=-I IR</JH4GK-I KL F"H ("J";RI- "(4,- # ;k4=,4K< -= 2H"=,-I GK"=J4J/I s 2H"<<-Itj R2 2. R4 R1. N H 4. R4. R3. R3 O. R2. R1. R3. R1. R2 R7. N H 10. R3. R6. NaBH4. O. R1. R4 N H 13. OH. R2. NH HN. catalyseur acide. 12. R5 R2. R3. R1. R4 N H. catalyseur acide. R3 R2. R7. R4 R5. NH HN R1. 14. R6. . ($/ YH=08(#7"!"!)4=662/$8( 0"7. -I ,4FRHH@</J3"=-I ,4IIR</JH4GK-I I@=J @'J-=KI # F"HJ4H ,kK= o"(R;FRHH@;- KJ H/,K4J )0 7)89 -= ";(@@; KMg IKH ;-GK-; I- (@=,-=I- K= ,-KQ4.<- FRHH@;- -= ("J";RI- "(4,-j -I ,4FRHH@</J3"=-I F-KO-=J 0JH- ;-I (4';-I H-(3-H(3/-Ig @K '4-= ,-I 4=J-H</,4"4H-I ,- IR=J3.I- ,- j = -11-Jg ;- ,4FRHH@</J3"=-KNF-KJ0JH-@QR,/-=KKj;k@H424=-g(-JJ-H/"(J4@="/J/H/";4I/-"O-( -;j @KJ-1@4Ig ;- (3;@HKH- 1-HH-KQ =/(-II4J- K= IK'IJH"J 3-Q"IK'IJ4JK/j -I ,/H4O/I GK4=@=4GK-I I@=J 2/=/H";-<-=J KJ4;4I/I F@KH ;-KH <-4;;-KH- J@;/H"=(- 1@=(J4@==-;;- s(3/<" tj k@QR,"=J ;- F;KI. . jo
(27) j--gjj4=,I-Rg"86 ("!620gKSSNg[Vg j jj"3"gj3"=";-:I3<4gj"=42K(34gj<'H@4I-gjj4=,I-Rg6'H62 H"7H":HLJJMg]gj. .
(28) -114("(- -IJ ;" g ";@HI GK- ;- 4o(3;@H"=4;- s@QR,"=J <@4=I FK4II"=Jt F-KJ 0JH- FH/1/H/ F@KH I" H/"(J4O4J/F;KI,@K(-j R3 R2. R7. R4 R5. NH HN R1. DDQ ou p-chloranile. R6. 14. R7. R3 R2. NH R1. 11. R4 R5. N R6. . ($/ ZH<=! 8)20!I90!)4=662/$8( 0""0. = ,/=@<'H- F;KI ,- <@;/(K;-I H/1/H-=(/-I ,"=I ;" ;4JJ/H"JKH- (@=J-="=J ;- <@J41 ,4FRHH@</J3.=-K,"=I;-KHIJHK(JKH-j-(4,/<@=JH-;-JH.I;"H2-(3"<F,k"FF;4("J4@=,-Ig-J ,-I<@;/(K;-IGK4(@=J4-==-=J(-<@J41iF@HF3RH4=-Ig(@<F;-Q-Ig I}g-J(j . . . @KH(-i(4 4=,-HgK4;;-Jj. .
(29) -'!1 ?32'*'1 2'-, !1 '.600-+#2&",!1 -I I F-KO-=J 0JH- KJ4;4I/I ,4H-(J-<-=J (@<<- ;42"=,I F@KH ;" IR=J3.I- ,- (@<F;-Q-I ,- (@@H,4="J4@=g(@<<-,/(H4JIKH;"F"HJ4-,H@4J-,K(3/<"j. Synthèse de complexes. Synthèse de ligands. N. HN. N. HN. N. HN. R NH. N. N. B. N. F F Calixphyrine. Bis-dipyrrométhène. NH. BODIPY. N NH. NH HN. N. N. DPM. N. Métallo complexes. Corrole. N NH. HN. N. N. N N. N. N. N. N N n. Porphyrine. Polymères de coordination (MOF). ($/ [H6)0 )4 ."798).)7 8)207!"7:"67. 7=08(#7"!".)' 0!729!" 2/4."<"7. -I I} s@H@= HH@<-J3-=-It H-FH/I-=J-=J K=- ,-I O@4-I ,k"FF;4("J4@= FH4=(4F";-I ,-I j = s;- } I-H" @<4I F"H ;" IK4J-t -IJ ("H"(J/H4I/ F"H ;" (@<F;-Q"J4@= ,kK= "J@<- ,- '@H- F"H ;-I "S@J-I ,kK= j - (@<F;-Q- @'J-=K F@HJ- 2/=/H";-<-=J K= 2H@KF-<-=J ,41;K@H@'@HR;- j -I (@<F@I/I FH/I-=J-=J ,-I FH@FH4/J/I @FJ4GK-I K=4GK-Ig F"HJ4(K;4.H-<-=J ,- . l }m,/F@I/F"H =O4JH@2-=j. .
(30) 1;K@H-I(-=(-j ;k4=IJ"H ,K '@H-g K= JH.I 2H"=, =@<'H- ,- </J"KQ F-KO-=J 0JH- (@<F;-Q/I "KQ I F@KH 1@KH=4H ;-I </J";;@ (@<F;-Q-I (@HH-IF@=,"=JIj -KQo(4 F@II.,-=J =@J"<<-=J ,-I "FF;4("J4@=I -= ("J";RI- @K -= ;K<4=-I(-=(-j " (@<F;-Q"J4@= F-KJ 0JH- H/";4I/- # F"HJ4H ,kK= FH/o1@=(J4@==";4I/"R"=JF;KI4-KHII4J-I,-(@@H,4="J4@=j-JRF-,-;42"=,F-H<-J,k"((/,-H# ,-IF@;R<.H-I,-(@@H,4="J4@=g-JF@J-=J4-;;-<-=J,-I s-J";oH2"=4( H"<-P@H:Itj@KJ- (-JJ- F"HJ4- (@=(-H="=J ;-I (@<F;-Q-I ,-I I -J ;-KHI "FF;4("J4@=I I-H" ,/O-;@FF/- ,"=I K= I-(@=,J-<FIj =- FH-<4.H- F"HJ4- F;KI 'H.O- I-H" (@=I"(H/- # ,/(H4H- ;kKJ4;4I"J4@= ,-I I (@<<- 4=J-H</,4"4H-I#;"IR=J3.I-,k"KJH-I;42"=,Ig=@J"<<-=J<"(H@(R(;4GK-I,/(H4JIIKH;-';@(2"K(3- ,K(3/<"j. !1 -++!',2!0+# ' '0!1 !16,2&"1! '1@ '.600-+#2&",!1!2 -00-*!1 -I (@HH@;-I I@=J ,-I ;42"=,I J/JH"FRHH@;4GK-I "H@<"J4GK-I F@II/,"=J K=4J/I FRHH@;4GK-I -J "J@<-I,-("H'@=-/$72j-I;42"=,II@=JH-=(@=JH/I,"=I;"="JKH-g1H/GK-<<-=JI@KI 1@H<-,- (@<F;-Q-,-(@'";JgJ-;;-GK-;"O4J"<4=-j -I,4FRHH@</J3.=-Ig-JF;KIF"HJ4(K;4.H-<-=J;-I'4Io,4FRHH@</J3.=-IgF-KO-=J0JH-KJ4;4I/I(@<<- FH/(KHI-KHI#;"IR=J3.I-,-;42"=,I<"(H@(R(;4GK-IgJ-;IGK-;-I(@HH@;-I@K;-IF@HF3RH4=-Ijg-I '4IoI -J ;-I (@HH@;-I I-H@=J ,/O-;@FF/I ,"=I K= FH-<4-H J-<FIg -J ;-I F@HF3RH4=-I ,"=I ;- FH@(3"4=F"H"2H"F3-j -I '4IoI I@=J ,-I <@;/(K;-I @L ,-KQ ,4FRHH@</J3.=-I I@=J ;4/Ij ;I F-KO-=J 0JH- ;4/I F"H ;-I F@I4J4@=I α @K βg "O-( ,-I -IF"(-KHI @K ,4H-(J-<-=Jj "=I K= FH-<4-H J-<FIg =@KI (@=I4,/H-H@=I;-I'4IoII"=I-IF"(-KHIKP g;4/IF"H;-IF@I4J4@=Iαgαks'4FRHH@;-Itj ;I I@=J @'J-=KI # F"HJ4H ,- ,-KQ 4,-=J4GK-I (@<F;-Q/I "KJ@KH ,kK= </J";g 2/=/H";-<-=J ;- =4(:-; s(3/<" tjgg -JJ- J-(3=4GK- F-H<-J ;" (H/"J4@= ,K F@=J αgαk -=JH- ;-I ,-KQ F"H . j@K,-JgjKH2-IIg("/H":jLJJQgWV]g j jj
(31) -==-IIRgjj-J;-Rg )"0 "gLJKMgYZVgj j"K,H@=g .8206 07jLJKMgZXg j j4"@gjo j34=gjj"JH4(:gj@;F34=g("/H2//90jLJJSg j j":"<@J@gj P"I34<"gjIK(34R"gj@R@,"gj"JIK@:"gj jC2-;gjKI":"gj
(32) @I34:@gj "24gj
(33) "2"R"<"g
(34) j4I343"H"E
(35) H 8"6H("/HgLJKOgYgj j 4-,R:gj @;4IS-PI:"gj HR:@g("/H2 H":jLJKOgZZgj jHCH4=2g jH/24-HgjHN2-Hgj;--'-H2g96H
(36) H 026'H("/jLJJRgj
(37) jK114=gjj"K,H@=gj";"S"Ho-=,@S"gj j
(38) @II-4=4g("/H96H
(39) HLJKNgXVg j
(40) jj 4;;g j 4=2-Hg j@S4,"H-O4)g hSR,;@gjj(@JJg";
(41) H("/jLJJOgX_gj . .
(42) ;k@QR,"J4@=#;"j-=4(:-;-IJ-=IK4J-,/(@<F;-Q/F"HJH"4J-<-=J"GK-KQ"(4,-F@KH,@==-H;- '4IoLLj Ni(OAc)2 NH. N. DCM/MeOH 40%. N. N. DDQ. N. Toluène 65%. Ni N. N. N Ni. N. N. 1 15 CHCl3 80%. 1) HCl 2) Na2CO3. NH N. N HN. . 16a. ($/ \H=08(#7"!I90 )7M7 074208/$72. =g J@"8 .H@=JIR=J3/J4I/;-FH-<4-H=@H(@HH@;--=J4.H-<-=J("H"(J/H4I/j'J-=KI@KI1@H<- ,-(@<F;-Q-,-=4(:-;g(-<"(H@(R(;-#/;-(JH@=I-IJ"=J4"H@<"J4GK-j ;-IJ(-F-=,"=JI-=I4';-# ;k@QR,"J4@=-JF-KJ1@H<-H#;k"4H;k@Q"(@HH@;-js(3/<"t Mes. N N Br Br N. . Br Br. Ni. Mes. Mes NiCl2, PPh3 Zn. N. N Ni. DMF 90%. N. N. Ni. N. N. Mes. Mes. N. N. O2. O N. Mes. Norcorrole. Oxacorrole. . ($/ ]H=08(#7"!9026 2662.". -'4Io,4FRHH@</J3.=-F@=J/KP -IJIR=J3/J4I/#F"HJ4H,K,4FRHH@</J3"=-,"=I;-I(@=,4J4@=I ,- (@=,-=I"J4@=,/(H4J-I"KF"H"O"=Js(3/<"tj"H/"(J4@=H/";4I/--=<4;4-K"(4,-,@==-;-(@<F@I/ KP I@KI1@H<-,-I-;,43R,H@'H@<4GK-s(3/<"tj . HBr N H. NH HN. CHO. MeOH 91%. NH HN 2 HBr N N 16b.2HBr. . ($/ ^H=08(#7"!I90 )7M4208$ X. . j J@g j
(43) "R"I34gj34<4SKgjo j34=gj@'"R"I34g
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(45) - F;KI 2/=/H";-<-=Jg ;k"((.I "KQ (@HH@;-I I- 1"4J # F"HJ4H ,kK= 4=J-H</,4"4H- J/JH"FRHH@;4GK- KQ F@II/,"=J ;-I JH@4I F@=JI /$72 4=I"JKH/Ij - J/JH"FRHH@;- (R(;4I- -= (@=,4J4@=I @QR,"=J-I F@KH ,@==-H;-(@HH@;-KR(@HH-IF@=,"=Js(3/<"tj Ph. Ph DDQ. NH HN Ph. Ph NH HN. Toluène 82%. HN. N. Ph. Ph NH HN. 17. 18. . ($/ _H=08(#7"979".."!"7 2662."7. 4=I4g ;-I '4IoI F-H<-JJ-=J ;k"((.I # ,-I ;42"=,I <"(H@(R(;4GK-I J-;I GK- ;-I (@HH@;-I @K ;-I F@HF3RH4=-Ig <"4I 4;I F@II.,-=J /2";-<-=J ,-I "FF;4("J4@=I -= (34<4- ,- (@@H,4="J4@=g F@KH ;" IR=J3.I-,- =@J"<<-=Jg,/O-;@FF/-K;J/H4-KH-<-=Jj. -0.&60',!1 -I F@HF3RH4=-I I@=J ,-I ;42"=,I J/JH"FRHH@;4GK-I "H@<"J4GK-I (@<F@I/I ,- GK"JH- K=4J/I FRHH@;4GK-I ;4/-I F"H GK"JH- F@=JI </J3.=-Ij 4=I4 GK- F@KH ;-I ,4FRHH@</J3.=-Ig 4I(3-H " /J/ F4@==4-H ,"=I ;" IR=J3.I- ,-I F@HF3RH4=-Ij -I FH-<4.H-I IR=J3.I-I 1KH-=J ,/(H4J-I # F"HJ4H ,- ,4FRHH@</J3.=-I αo'H@</I H/"24II"=J "O-( ,-I αo</J3R;/I # JH.I 3"KJ- J-<F/H"JKH- s ~tj-JJ-</J3@,-F-H<-J,k@'J-=4HKS-JLJ"O-(K=-IR</JH4-H/,K4J-s(3/<"tjKII4g;-I F@I4J4@=I/$72=-I@=JF"IIK'IJ4JK/-IF"H(-JJ-</J3@,-j. . jR,4=gj-<-;;4gj=";-H@2;Kg96H
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