Perfluorinated Ligands Induce Meridional Metal ... - ACS Publications

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Perfluorinated ligands induce meridional metal stereochemistry to generate ML , M L and M L prisms 8

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Marion Kieffer, Ben S. Pilgrim, Tanya K Ronson, Derrick A. Roberts, Mina Aleksanyan, and Jonathan R. Nitschke J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.6b02445 • Publication Date (Web): 04 May 2016 Downloaded from http://pubs.acs.org on May 4, 2016

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Journal of the American Chemical Society

3HUIOXRULQDWHG OLJDQGV LQGXFH PHULGLRQDO PHWDO VWHUHRFKHPL VWU\ WR JHQHUDWH 0 / 0 / DQG 0 / SULVPV ƒ”‹‘• ‹‡ˆˆ‡”á ‡• ä ‹Ž‰”‹•á ƒ•›ƒ ä ‘••‘•á –Šƒ• ä ‹–•…Š•‡

‡””‹…• ä ‘„‡”–•á

‡’ƒ”–•‡•– ‘ˆ Š‡•‹•–”›á •‹˜‡”•‹–› ‘ˆ ƒ•„”‹†‰‡á ‡••ˆ‹‡Ž† ‘ƒ†á ƒ•„”‹†‰‡

‹•ƒ Ž‡••ƒ•›ƒ• ƒ•† ‘•ƒæ ^]

á

•‹–‡† ‹•‰†‘•

ã ‡”‹†‹‘•ƒŽ •‡” …‘‘”†‹•ƒ–‹‘• ’”‘•‘–‡• –Š‡ ‰‡•‡”ƒ–‹‘• ‘ˆ Žƒ”‰‡” ƒ•† Ž‘™‡”æ•›••‡–”› ’”‹••ƒ–‹… •‡–ƒŽŽ‘•—æ ’”ƒ•‘Ž‡…—Žƒ” •–”—…–—”‡•á ‹• …‘•–”ƒ•– ™‹–Š –Š‡ ˆƒ…‹ƒŽ ˆƒ… …‘‘”†‹•ƒ–‹‘• …‘••‘• –‘ ••ƒŽŽ‡” ƒ•† Š‹‰Š‡”æ•›••‡–”› ’‘Ž›Š‡æ †”ƒä ‡”‡ ™‡ †‡•…”‹„‡ ƒ ‰‡•‡”ƒŽ ”‘—–‡ –‘ –Š‡ •‡Ž‡…–‹˜‡ ˆ‘”•ƒ–‹‘• ‘ˆ Žƒ”‰‡ •‡–ƒŽŽ‘•—’”ƒ•‘Ž‡…—Žƒ” ’”‹••• –Šƒ– …‘•–ƒ‹• ‡š…Ž—æ •‹˜‡Ž› •‡” …‘‘”†‹•ƒ–‡† •‡–ƒŽ ˜‡”–‹…‡•ä Š‡ —•‡ ‘ˆ ^æˆ‘”•›Ž’›”‹†‹•‡ •—„…‘•’‘•‡•–• –Šƒ– …‘•–ƒ‹• ’‡”ˆŽ—‘”‘’Š‡•›Ž‡•‡ •—„•æ –‹–—‡•–• ƒ– –Š‡‹” aæ’‘•‹–‹‘•• ”‡•—Ž–‡† ‹• •–‡”‡‘•‡Ž‡…–‹˜‡ ˆ‘”•ƒ–‹‘• ‘ˆ –Š‡ ‹”‘• …‘•’Ž‡š‡• ˆ”‘• –Š‡•‡ •—„…‘•’‘•‡•–•ä •Ž› •‡” ˜‡”–‹…‡• ™‡”‡ ‘„•‡”˜‡†á ƒ• ‘’’‘•‡† –‘ –Š‡ •–ƒ–‹•–‹…ƒŽ ˆƒ… •‡” •‹š–—”‡ ‘–Š‡”™‹•‡ ‰‡•‡”ƒ–‡†ä Š‹• •‡”æ•‡Ž‡…–‹˜‡ •‡Žˆæƒ••‡•„Ž› …‘—Ž† „‡ —•‡† –‘ ’”‡’ƒ”‡ –‡–”ƒ‰‘•ƒŽ d ]^ á ’‡•–ƒ‰‘•ƒŽ ]\ ]a ƒ•† Š‡šƒ‰‘•ƒŽ ]^ ]d ’”‹•••á „› –ƒ•‹•‰ ƒ†˜ƒ•–ƒ‰‡ ‘ˆ –Š‡ •—„–Ž‡ •‡Ž‡…–‹˜‹–‹‡• ‹•’‘•‡† „› –Š‡ †‹ˆˆ‡”‡•– ƒ•‹Ž‹•‡• ƒ•† …‘—•–‡”‹‘•• ‡•’Ž‘›‡†ä Š‡ ‡“—‹Ž‹„”‹—• „‡æ –™‡‡• –Š‡ –‡–”ƒ‰‘•ƒŽ ƒ•† ’‡•–ƒ‰‘•ƒŽ ’”‹•• ˆ‘ŽŽ‘™‡† ƒ Ž‹•‡ƒ” ˆ”‡‡ ‡•‡”‰› ”‡Žƒ–‹‘••Š‹’á ™‹–Š –Š‡ ”ƒ–‹‘ „‡–™‡‡• •–”—…–—”‡• …‘””‡Žƒ–‹•‰ ™‹–Š –Š‡ ƒ••‡–– W’Æ ’ƒ”ƒ•‡–‡” ‘ˆ –Š‡ ‹•…‘”’‘”ƒ–‡† ƒ•‹Ž‹•‡ä Š‡ …‘•–”ƒ•–‹•‰ ’”‡ˆ‡”‡•…‡• ‘ˆ –Š‡ ˆŽ—‘”‹•ƒ–‡† ƒ•† •‘•æˆŽ—‘”‹•ƒ–‡† Ž‹‰ƒ•†• –‘ ‰‡•‡”ƒ–‡ ’”‹••• ƒ•† –‡–”ƒŠ‡†”ƒ ”‡•’‡…–‹˜‡Ž› ™‡”‡ “—ƒ•–‹ˆ‹‡† ‡•‡”‰‡–‹…ƒŽŽ›á ™‹–Š –Š‡ †‡•–ƒæ „‹Ž‹œƒ–‹‘• ‹•…”‡ƒ•‹•‰ Ž‹•‡ƒ”Ž› ˆ‘” ‡ƒ…Š ò‹•…‘””‡…– Ž‹‰ƒ•†ó ‹•…‘”’‘”ƒ–‡† ‹•–‘ ‡‹–Š‡” •–”—…–—”‡ä

‡…‡•– ƒ†˜ƒ•…‡• ‹• •—’”ƒ•‘Ž‡…—Žƒ” …Š‡•‹•–”› Šƒ˜‡ ’”‘†—…‡† ƒ Š‘•– ‘ˆ ‹•–”‹…ƒ–‡ •‡Žˆæƒ••‡•„Ž‡† ƒ”…Š‹–‡…–—”‡• ‘ˆ ‹•…”‡ƒ•‹•‰ •–”—…–—”ƒŽ] ƒ•† ˆ—•…–‹‘•ƒŽ …‘•’Ž‡š‹–›ä^ • …Š‡•‹…ƒŽ •‡Žˆæƒ••‡•„Ž› •‘˜‡• ˆ”‘• ƒ• ‡”ƒ ‘ˆ •‡”‡•†‹’‹–› ‹•–‘ ‘•‡ ‘ˆ ”ƒ–‹‘•ƒŽ †‡•‹‰•á^‡ ‡Ž—…‹†ƒ–‹‘• ‘ˆ –Š‡ ”—Ž‡• –Šƒ– ‰‘˜‡”• –Š‡ ƒ••‡•„Ž› ’”‘…‡•• „‡…‘•‡• ’”‘‰”‡••‹˜‡Ž› •‘”‡ ‹•’‘”–ƒ•–ä Š‡ •–”—…–—”‡• ‘ˆ †‹•…”‡–‡ •‡–ƒŽæ‘”‰ƒ•‹… …‘•æ ’Ž‡š‡• –Šƒ– ˆ‘”• ‹• •‘Ž—–‹‘• ƒ”‡ †‡–‡”•‹•‡† „› –Š‡ ‰‡‘æ •‡–”‹… ”‡Žƒ–‹‘••Š‹’ „‡–™‡‡• –Š‡ …‘‘”†‹•ƒ–‹‘• ’”‡ˆ‡”‡•…‡• ‘ˆ –Š‡ •‡–ƒŽ ƒ•† Ž‹‰ƒ•† …‘•’‘•‡•–•á_ „—– ƒŽ•‘ ‹•ˆŽ—‡•…‡† „› ˆƒ…–‘”• •—…Š ƒ• •‘Ž˜ƒ–‹‘•á` …‘•…‡•–”ƒ–‹‘•áa –Š‡ ”ƒ–‹‘ „‡–™‡‡• …‘•’‘•‡•–•áb –Š‡ ’”‡•‡•…‡ ‘ˆ ‰—‡•–• ‘” –‡•æ ’Žƒ–‡•ác ƒ•† ‡š’‘•—”‡ –‘ ‡š–‡”•ƒŽ •–‹•—Ž‹ •—…Š ƒ• Ž‹‰Š–äd ‹”‡…–‹•‰ –Š‡ ƒ••‡•„Ž› ‘ˆ •—„…‘•’‘•‡•–• ‹•–‘ ƒ †‡•‹”‡† •–”—…–—”‡ ”‡“—‹”‡• …‘•–”‘Ž ‘˜‡” –Š‡ …‘•’Ž‡š ‹•–‡”’Žƒ› „‡–™‡‡• –Š‡•‡ ˆƒ…–‘”•äe ‘•‘Ž‡’–‹… –Š”‡‡æ†‹•‡••‹‘•ƒŽ ƒ••‡•„Ž‹‡• ‡•…‘•’ƒ•• •–”—…–—”ƒŽ –›’‡• ‹•…Ž—†‹•‰ –Š‡ Žƒ–‘•‹… •‘Ž‹†• •—…Š ƒ• –Š‡ –‡–”ƒŠ‡†”‘•á]\ …—„‡]] ƒ•† ‹…‘•ƒŠ‡†”‘•á]ˆ ƒ•† ”…Š‹•‡†‡ƒ• •‘Ž‹†• •—…Š ƒ• –Š‡ –”—•…ƒ–‡† –‡–”ƒŠ‡†”‘•á]^ ]_ ]` …—„‘…–ƒŠ‡†”‘• ƒ•† ”Š‘•„‹…—„‘…–ƒŠ‡†”‘•ä Š‡ ˆ‘”•ƒæ –‹‘• ‘ˆ –Š‡ •‹•’Ž‡•– ‘ˆ –Š‡•‡á –Š‡ –‡–”ƒŠ‡†”‘•á ‹• ™‡ŽŽ ’”‡æ …‡†‡•–‡†ä]\ ‘™‡˜‡”á –Š‡ •‡Ž‡…–‹˜‡ ˆ‘”•ƒ–‹‘• ‘ˆ •‘”‡ …‘•’Ž‡šá Š‹‰Š‡” •—…Ž‡ƒ”‹–› •–”—…–—”‡• ‹• Ž‡•• …‘••‘•ä ˆ –Š‡•‡á –Š‡ ’”‹••ƒ–‹… •–”—…–—”‡•]a ƒ”‡ ‘ˆ ’ƒ”–‹…—Žƒ” ‹•–‡”‡•–á ƒ• –Š‡› …ƒ• ˆ‡ƒ–—”‡ ™‡ŽŽæ†‡ˆ‹•‡† …›Ž‹•†”‹…ƒŽ ’‘”‡• ”‡•‹•‹•æ …‡•– ‘ˆ „‘–Š •ƒ–—”ƒŽ]b ƒ•† •›•–Š‡–‹… ‹‘• …Šƒ••‡Ž•ä]c ‘™æ

‡˜‡”á –Š‡”‡ ƒ”‡ ˆ‡™ ”—Ž‡• –‘ ‰—‹†‡ –Š‡ †‡•‹‰• ‘ˆ ’”‹••ƒ–‹… ƒ”…Š‹–‡…–—”‡• ™‹–Š …Šƒ••‡Ž• ‘ˆ ˜ƒ”›‹•‰ †‹•‡••‹‘••ä ‘”‡ ”‘„—•– ”ƒ–‹‘•ƒŽ †‡•‹‰• ’”‹•…‹’Ž‡• ƒ”‡ –Š‡”‡ˆ‘”‡ ˜‹–ƒŽ ˆ‘” ”‡ƒŽ‹œ‹•‰ –Š‡ ’‘–‡•–‹ƒŽ ƒ’’Ž‹…ƒ–‹‘•• ‘ˆ –Š‡•‡ •‡Žˆæ ƒ••‡•„Ž‡† ƒ”…Š‹–‡…–—”‡•ä ‡•’‹–‡ –Š‡ •‹•‹Žƒ”‹–› „‡–™‡‡• –Š‡ …‘‘”†‹•ƒ–‹‘• ˜‡…–‘” ”‡Žƒ–‹‘••Š‹’•]d ”‡“—‹”‡† –‘ ˆ‘”• –‡–”ƒŠ‡†”ƒ ƒ•† ’”‹•••á –Š‡ •ƒŒ‘”‹–› ‘ˆ „‹•æ’›”‹†›Ž‹•‹•‡ Ž‹‰ƒ•†• ‹•˜‡•–‹‰ƒ–‡† „› ‘—” ‰”‘—’ ƒ••‡•„Ž‡† ‡š…Ž—•‹˜‡Ž› ‹•–‘ –‡–”ƒŠ‡†”ƒŽ •–”—…æ –—”‡• ™Š‡• …‘•„‹•‡† ™‹–Š ‘…–ƒŠ‡†”ƒŽ •‡–ƒŽ …‡•–‡”•ä]e Š‡ ˆ‘”•ƒ–‹‘• ‘ˆ ’”‹••ƒ–‹… ƒ”…Š‹–‡…–—”‡• ™ƒ• ‘„•‡”˜‡† ‘•Ž› ‹• •’‡…‹ˆ‹… •‘Ž˜‡•– •‹š–—”‡•`… ‘” ‹• –Š‡ ’”‡•‡•…‡ ‘ˆ ƒ –‡•’Žƒ–‹•‰ ƒ•‹‘•ä^\ ˜‡• –Š‡•á –Š‡•‡ ’”‹••• ‹• •ƒ•› …ƒ•‡• ‡š‹•–‡† ‹• ‡“—‹Ž‹„”‹—• ™‹–Š –Š‡ …‘””‡•’‘•†‹•‰ –‡–”ƒŠ‡†”ƒä ‡–”ƒŠ‡†”ƒŽ •–”—…–—”‡• ƒ”‡ …Šƒ”ƒ…–‡”‹œ‡† „› –Š‡ ˆƒ…‹ƒŽ ˆƒ… …‘‘”†‹•ƒ–‹‘• ‘ˆ –Š‡•‡ Ž‹‰ƒ•†• ™Š‡”‡ –Š‡ –Š”‡‡ ‹•‹•‡ •‹–”‘‰‡• ƒ–‘•• †‡ˆ‹•‡ ‘•‡ –”‹ƒ•‰—Žƒ” ˆƒ…‡ ‘ˆ –Š‡ ‘…–ƒŠ‡æ †”ƒŽ …‘‘”†‹•ƒ–‹‘• •’Š‡”‡ á^] ™Š‡”‡ƒ• –Š‡ ’”‹••ƒ–‹… •–”—…æ –—”‡• ’‘••‡•• •‡”‹†‹‘•ƒŽ •‡” …‘‘”†‹•ƒ–‹‘• ™Š‡”‡ –Š‡ –Š”‡‡ ‹•‹•‡ •‹–”‘‰‡• ƒ–‘•• †‡ˆ‹•‡ ƒ ’Žƒ•‡ –Šƒ– ‹•…Ž—†‡• –Š‡ •‡–ƒŽ …‡•–‡” ä Š‡”‡ˆ‘”‡á ™‡ ’‘•–—Žƒ–‡† –Šƒ– –Š‡ —•‡ ‘ˆ Ž‹‰ƒ•†• –Šƒ– ‡šŠ‹„‹– ƒ …Ž‡ƒ” ’”‡ˆ‡”‡•…‡ ˆ‘” –Š‡ ˆ‘”•ƒ–‹‘• ‘ˆ •‡” ˜‡”–‹…‡• ™‘—Ž† ˆƒ…‹Ž‹–ƒ–‡ –Š‡ •‡Ž‡…–‹˜‡ ˆ‘”•ƒ–‹‘• ‘ˆ •‘˜‡Ž ’”‹••ƒ–‹… ƒ”…Š‹–‡…–—”‡• ‘˜‡” –Š‡ •‘”‡ ˆ”‡“—‡•–Ž›æ ‘„•‡”˜‡† –‡–”ƒŠ‡†”ƒä ‡•…‡á ™‡ •‡– ‘—– –‘ ‡š’Ž‘”‡ ˆƒ…–‘”• ”‡•’‘••‹„Ž‡ ˆ‘” ‰‡•‡”ƒ–‹•‰ •‡” …‘‘”†‹•ƒ–‹‘• ‹• –”ƒ••‹–‹‘• •‡–ƒŽ …‘•’Ž‡š‡• –Šƒ– ‹•…‘”’‘”ƒ–‡ –Š‡ ˜‡”•ƒ–‹Ž‡ ^æ ’›”‹†›Ž‹•‹•‡ Ž‹‰ƒ•† •‘–‹ˆä

ACS Paragon Plus Environment


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Š‡ …‘•–”ƒ•–‹•‰ ’”‡ˆ‡”‡•…‡ ‘ˆ •—„…‘•’‘•‡•–• ƒ•† –‘ ˆ‘”• ‘•Ž› –‡–”ƒŠ‡†”ƒŽ ‘” ’”‹••ƒ–‹… •–”—…–—”‡• ”‡•’‡…æ –‹˜‡Ž› ™ƒ• ’”‘„‡† ˆ—”–Š‡” ‹• ‡š’‡”‹•‡•–• ‡•’Ž‘›‹•‰ •‹šæ –—”‡• ‘ˆ –Š‡ –™‘ •—„…‘•’‘•‡•–•ä • „‘–Š •—„…‘•’‘•‡•–• Šƒ˜‡ •‡ƒ”Ž› ‹†‡•–‹…ƒŽ Ž‡•‰–Š•á ™‡ ‡š’‡…–‡† –Š‡• –‘ •‹š –‘ ˆ‘”• ƒ Ž‹„”ƒ”› ‘ˆ Š‡–‡”‘Ž‡’–‹… ƒ••‡•„Ž‹‡• ‹ˆ •‡‹–Š‡” Ž‹‰ƒ•† Šƒ† ƒ †‹•–‹•…– ’”‡ˆ‡”‡•…‡ ˆ‘” ‡‹–Š‡” •–”—…–—”ƒŽ –›’‡ä ˆ •‹š‡† ‹• ‡“—ƒŽ ƒ•‘—•–•á ƒ †‡˜‹ƒ–‹‘• ˆ”‘• –Š‡ ‡•–”‘’‹…ƒŽæ Ž›æˆƒ˜‘”‡† •–ƒ–‹•–‹…ƒŽ „‹•‘•‹ƒŽ †‹•–”‹„—–‹‘• ‘ˆ Š‡–‡”‘Ž‡’æ –‹… ƒ••‡•„Ž‹‡•á ‡˜‡• ‹• –Š‡ ƒ„•‡•…‡ ‘ˆ …‘•’Ž‡–‡ •ƒ”…‹••‹•æ –‹… •‡Žˆæ•‘”–‹•‰á^d ™‘—Ž† ‹•†‹…ƒ–‡ ƒ• ‹•Š‡”‡•– ’”‡ˆ‡”‡•…‡ ˆ‘” –Š‡ Ž‹‰ƒ•†• –‘ •‡Žˆæ•‘”– ‹•–‘ –Š‡‹” ’”‡ˆ‡””‡† •–”—…–—”ƒŽ –›’‡ä

‹‰—”‡ _ä æ ‘ˆ ƒ •‹š–—”‡ ‘ˆ ’”‡ˆ‘”•‡† •–”—…–—”‡• _ ƒ•† `ƒ ‹• ƒ ^ã] ”ƒ–‹‘ ƒˆ–‡” ‡“—‹Ž‹„”ƒ–‹‘• ƒ– a\ Ó ˆ‘” ‘•‡ ™‡‡•ä

‡–”ƒŠ‡†”ƒŽ …ƒ‰‡ _ ƒ•† –‡–”ƒ‰‘•ƒŽ ’”‹•• `ƒ ™‡”‡ …‘•æ „‹•‡† ‹• ƒ ^ã] ”ƒ–‹‘á ‰‹˜‹•‰ ƒ ]ã] ”ƒ–‹‘ „‡–™‡‡• –Š‡ •‘•æ ˆŽ—‘”‹•ƒ–‡† •—„…‘•’‘•‡•– ƒ•† ˆŽ—‘”‹•ƒ–‡† •—„…‘•’‘æ •‡•– ™‹–Š‹• –Š‡ •ƒ•’Ž‡ä Š‡ •‹š–—”‡ ™ƒ• Ž‡ˆ– –‘ ‡“—‹Ž‹æ „”ƒ–‡ ƒ– a\ Ó ˆ‘” ‘•‡ ™‡‡•ä Š‡ ] •’‡…–”—• ‘ˆ –Š‡ •‹š–—”‡ „‡…ƒ•‡ •‹‰•‹ˆ‹…ƒ•–Ž› •‘”‡ …‘•’Ž‡š †—”‹•‰ –Š‹• –‹•‡á „—– †‹† •‘– …Šƒ•‰‡ ˆ—”–Š‡”á ‹•†‹…ƒ–‹•‰ –Šƒ– –Š‡ •›•æ –‡• Šƒ† ”‡ƒ…Š‡† ‡“—‹Ž‹„”‹—•ä æ ”‡•—Ž–• ‹‰—”‡ _ ‹•†‹…ƒ–‡† –Š‡ ’”‡•‡•…‡ ‘ˆ ‡ ` b –‡–”ƒŠ‡†”ƒ ‹•…‘”’‘”ƒ–‹•‰ „‡–™‡‡• œ‡”‘ ƒ•† ˆ‘—” ˆŽ—‘”‹•ƒ–‡† ”‡•‹†—‡•á „—– •‘ –‡–”ƒŠ‡†”ƒ ‹•…‘”’‘”ƒ–‹•‰ ˆ‹˜‡ ‘” •‹šä ‡ƒ•• …‘””‡•’‘•†‹•‰ –‘ ‡ d ]^ –‡–”ƒ‰‘•ƒŽ ’”‹••• ‹•…‘”’‘”ƒ–‹•‰ „‡–™‡‡• œ‡”‘ ƒ•† •‹š •‘•æ ˆŽ—‘”‹•ƒ–‡† ”‡•‹†—‡• ™‡”‡ ƒŽ•‘ ‘„•‡”˜‡†á „—– •‘•‡ ‹•æ …‘”’‘”ƒ–‹•‰ •‘”‡ –Šƒ• •‹šä ‡•…‡á ƒ …Ž‡ƒ” †‡˜‹ƒ–‹‘• ˆ”‘• –Š‡ „‹•‘•‹ƒŽ †‹•–”‹„—–‹‘• ™ƒ• ‘„–ƒ‹•‡† ƒ…”‘•• „‘–Š ƒ”…Š‹æ –‡…–—”‡•ä Š‡ ‹•–”ƒ…–ƒ„‹Ž‹–› ‘ˆ –Š‡ ] •’‡…–”—• ™ƒ• –Š—• ‹•ˆ‡””‡† –‘ ”‡•—Ž– „‘–Š ˆ”‘• –Š‡ •ƒ•› †‹ˆˆ‡”‡•– …‘•æ ‰‡•‡”• ’”‡•‡•–á ƒ•† –Š‡ †‹ˆˆ‡”‡•– •–”—…–—”ƒŽ ƒ””ƒ•‰‡•‡•–• –Šƒ– •ƒ› „‡ ƒ†‘’–‡† „› •‘•‡ …‘•‰‡•‡”• ‡ä‰ä ‡` …` ^ ä ‡ ‹•ˆ‡” –Šƒ– ™Š‡• ‘„•‡”˜‹•‰ …Ž—•–‡”• ‘ˆ æ ’‡ƒ••á ™Š‡”‡ ƒŽŽ •‹‰•ƒŽ• …‘””‡•’‘•† –‘ •–”—…–—”‡• ™‹–Š ƒ …‘••‘•

•–”—…–—”‡ –›’‡ ‡‹–Š‡” –‡–”ƒŠ‡†”ƒ _ ‘” –‡–”ƒ‰‘•ƒŽ ’”‹••• ` ‹• ƒ •‹•‰Ž‡ …Šƒ”‰‡ •–ƒ–‡á –Š‡ ”‡•’‘••‡ ˆƒ…–‘”• ’‡ƒ• ‹•–‡••‹–‹‡• ™‡”‡ ‹•†‡’‡•†‡•– ‘ˆ –Š‡ •—•„‡” ‘ˆ ˆŽ—‘”‹æ •ƒ–‡† Ž‹‰ƒ•†• ’”‡•‡•– ‹• ‡ƒ…Š –‡–”ƒŠ‡†”‘•á ‘” ™Š‹…Š •–”—…æ –—”ƒŽ ‹•‘•‡” ™ƒ• ’”‡•‡•–ä Š—•á –Š‡ …‘•…‡•–”ƒ–‹‘• ‘ˆ ‡ƒ…Š ‘ˆ –Š‡ …‘•‰‡•‡”• ™ƒ• …‘••‹†‡”‡† –‘ „‡ ’”‘’‘”–‹‘•ƒŽ –‘ –Š‡ ‹•–‡••‹–› ‘ˆ ‹–• • œ ’‡ƒ•á ƒ•† –Š‡ ”‡Žƒ–‹˜‡ ’”‘’‘”–‹‘•• ‘ˆ •’‡…‹‡• †‹ˆˆ‡”‹•‰ ‘•Ž› ‹• –Š‡ •—•„‡” ‘ˆ ˆŽ—‘”‹•ƒ–‡† Ž‹‰ƒ•†• ‹•…‘”’‘”ƒ–‡† ™‡”‡ †‡–‡”•‹•‡† „› •‡ƒ•—”‹•‰ –Š‡ †‹ˆˆ‡”æ ‡•…‡• ‹• ’‡ƒ• ‹•–‡••‹–‹‡•ä Š‹• •‡–Š‘† Šƒ• ’”‘˜‹†‡† …‘•æ •‹•–‡•– ”‡•—Ž–• ‹• –Š‡ …‘•–‡š– ‘ˆ ‘–Š‡” …‘•’Ž‡š •‡–ƒŽŽ‘•—æ ’”ƒ•‘Ž‡…—Žƒ” ƒ”…Š‹–‡…–—”‡•äê ‹–Š‹• ‡ƒ…Š …Šƒ”‰‡ •–ƒ–‡á –Š‡ ‹•–‡••‹–‹‡• ‘ˆ –Š‡ • œ ’‡ƒ•• ™‡”‡ •‘”•ƒŽ‹œ‡†á ƒ•† –Š‡•‡ ‹•–‡••‹–‹‡• ™‡”‡ ƒ˜‡”æ ƒ‰‡† ƒ…”‘•• ƒŽŽ ‘„•‡”˜‡† …Šƒ”‰‡ •–ƒ–‡• –‘ ‰‹˜‡ –Š‡ ”‡Žƒ–‹˜‡ ƒ•‘—•–• ‘ˆ ‡ƒ…Š …‘•‰‡•‡” ‹• •‘Ž—–‹‘•ä Š‡•‡ ˜ƒŽ—‡• ™‡”‡ ’Ž‘––‡† ƒŽ‘•‰•‹†‡ –Š‡ „‹•‘•‹ƒŽ †‹•–”‹„—–‹‘• ‹‰—”‡ `ƒ ä • –Š‡ …ƒ•‡• ‘ˆ „‘–Š –‡–”ƒŠ‡†”ƒ _ ƒ•† –‡–”ƒ‰‘•ƒŽ ’”‹••• ` á •–”‘•‰ †‡˜‹ƒ–‹‘•• ™‡”‡ ‘„•‡”˜‡† ˆ”‘• „‹•‘•‹ƒŽ †‹•æ –”‹„—–‹‘•• ‘ˆ ’”‘†—…–• –Šƒ– ‹•…‘”’‘”ƒ–‡ „‘–Š •‹•†• ‘ˆ Ž‹‰ƒ•†• ‹‰—”‡• `ƒ ƒ•† `„á ”‡•’‡…–‹˜‡Ž› ä Š‡•‡ †‡˜‹ƒ–‹‘•• ”‡ˆŽ‡…–‡† –Š‡ ‡•‡”‰‡–‹… ’”‡ˆ‡”‡•…‡ ‘ˆ •‘•æˆŽ—‘”‹•ƒ–‡† •—„…‘•’‘•‡•– –‘ ˆ‘”• –‡–”ƒŠ‡†”‘• _ ƒ•† ˆŽ—‘”‹•ƒ–‡† •—„…‘•’‘•‡•– –‘ ˆ‘”• –‡–”ƒ‰‘•ƒŽ ’”‹•• `ƒä • ‘”†‡” –‘ “—ƒ•–‹ˆ› –Š‡•‡ ‡•‡”‰‡–‹… ’”‡ˆ‡”‡•…‡•á ƒ •‡– ‘ˆ ‡“—‹Ž‹„”‹—• …‘••–ƒ•–• ™‡”‡ …ƒŽ…—Žƒ–‡† „‡–™‡‡• …‘•‰‡•‡”• ‹• –Š‡ –‡–”ƒŠ‡†”ƒŽ •‡”‹‡•á „› •‡ƒ•—”‹•‰ –Š‡ ”ƒ–‹‘ „‡–™‡‡• –Š‡ ‘„•‡”˜‡† ’”‘’‘”–‹‘• ‘ˆ ‡ƒ…Š •’‡…‹‡• ƒ•† ‹–• ‡š’‡…–‡† ’”‘’‘”–‹‘•á „ƒ•‡† —’‘• ƒ „‹•‘•‹ƒŽ †‹•–”‹„—–‹‘• á ‡…æ –‹‘• `ä_ ˆ‘” †‡–ƒ‹Ž• ä Š‡ ”‡Žƒ–‹˜‡ ‡•‡”‰‹‡• „‡–™‡‡• …‘•æ ‰‡•‡”• ™‡”‡ †‡–‡”•‹•‡† ˆ”‘• –Š‡•‡ ‡“—‹Ž‹„”‹—• …‘•æ •–ƒ•–•ä Š‡•‡ ‹„„• ‡•‡”‰‹‡• ™‡”‡ ’Ž‘––‡† ”‡Žƒ–‹˜‡ –‘ –Š‡ „ƒ•‡Ž‹•‡ ‘ˆ ˆ—ŽŽ› •‘•æˆŽ—‘”‹•ƒ–‡† –‡–”ƒŠ‡†”ƒŽ …ƒ‰‡ _á ™Š‹…Š ™ƒ• †‡•–ƒ„‹Ž‹œ‡† „› ƒ• ƒ˜‡”ƒ‰‡ ‘ˆ `ä] • •‘ŽÇ] ˆ‘” ‡ƒ…Š ˆŽ—‘”‹•ƒ–‡† •—„…‘•’‘•‡•– ‹•…‘”’‘”ƒ–‡† ‹•–‘ –Š‡ –‡–”ƒæ Š‡†”ƒŽ …ƒ‰‡á ƒ• †‡–‡”•‹•‡† „› ƒ Ž‹•‡ƒ” Ž‡ƒ•–æ•“—ƒ”‡• ˆ‹– ‹‰—”‡ `… ä ‡ …ƒ••‘– †‹ˆˆ‡”‡•–‹ƒ–‡ „‡–™‡‡• •–”—…–—”ƒŽ ‹•‘•‡”• ˜‹ƒ æ á –Š‡”‡ˆ‘”‡ ‘•Ž› ƒ ™‡‹‰Š–‡† ƒ˜‡”ƒ‰‡ ‡•‡”‰› ™ƒ• …ƒŽ…—Žƒ–‡†ä ’’Ž›‹•‰ –Š‡ •ƒ•‡ ’”‘…‡†—”‡ –‘ –Š‡ –‡–”ƒ‰‘•ƒŽ ’”‹•• `ƒ ‹•†‹…ƒ–‡† –Šƒ– –Š‡ ‹•…‘”’‘”ƒ–‹‘• ‘ˆ ‡ƒ…Š •‘•æˆŽ—‘”‹•ƒ–‡† •—„…‘•’‘•‡•– ‹•…—””‡† ƒ• ƒ˜‡”ƒ‰‡ ‡•‡”‰‡–‹… †‡•–ƒ„‹Ž‹œƒ–‹‘• ‘ˆ ^äc • •‘ŽÇ]ä – ‹• –Š—• •‘”‡ ‡•‡”‰‡–‹…ƒŽŽ› …‘•–Ž› –‘ ‹•…‘”’‘”ƒ–‡ ƒ ˆŽ—‘”‹•ƒ–‡† Ž‹‰ƒ•† ‹•–‘ ƒ –‡–”ƒŠ‡†”‘• –Šƒ• ƒ •‘•æ ˆŽ—‘”‹•ƒ–‡† Ž‹‰ƒ•† ‹•–‘ ƒ –‡–”ƒ‰‘•ƒŽ ’”‹••á ™Š‹…Š ‹• …‘•æ •‹•–‡•– ™‹–Š –Š‡ ‘„•‡”˜ƒ–‹‘• –Šƒ– •‘•‘•—…Ž‡ƒ” …‘•’Ž‡š ] ˆ‘”•‡† ƒ• ƒ •–ƒ–‹•–‹…ƒŽ ˆƒ…æ•‡” •‹š–—”‡á ™Š‡”‡ƒ• •‡”æ^ ˆ‘”•‡† •–‡”‡‘•‡Ž‡…–‹˜‡Ž›ä Š‡ ”‡Žƒ–‹˜‡ …‘•–”‹„—–‹‘•• ‘ˆ ‡•–”‘’› ƒ•† ‡•–ŠƒŽ’› –‘ –Š‡ –‡–”ƒŠ‡†”‘•æ’”‹•• ‡“—‹Ž‹„”‹ƒ …ƒ••‘– „‡ “—ƒ•–‹ˆ‹‡† „ƒ•‡† —’‘• –Š‡ †ƒ–ƒ ƒ˜ƒ‹Žƒ„Ž‡á ƒ•† ƒ •‡ƒ•‹•‰ˆ—Ž ˜ƒ• î– ‘ˆˆ ƒ•ƒŽ›•‹• ‹• ’”‡…Ž—†‡† „› –Š‡ •Ž‘™æ •‡•• ‘ˆ ‡“—‹Ž‹„”ƒ–‹‘• „‡Ž‘™ a\ Ó á ƒ•† „”‘ƒ†‡•‹•‰ ‘ˆ –Š‡ ] •’‡…–”—•á …‘••‹•–‡•– ™‹–Š ’‘••‹„Ž‡ •ƒ•’Ž‡ †‡æ ‰”ƒ†ƒ–‹‘•á ƒ„‘˜‡ c\ Ó ä •–”‘’› –‡•†• –‘ ˆƒ˜‘”• –Š‡ ˆ‘”•ƒæ –‹‘• ‘ˆ •–”—…–—”‡• ™‹–Š –Š‡ •‹•‹•—• •—•„‡” ‘ˆ …‘•’‘æ •‡•–•_ƒáaƒ ƒ•† ‹• –Š‹• …ƒ•‡ –Š‡ –‡–”ƒŠ‡†”‘• ‹•…‘”’‘”ƒ–‡• ŠƒŽˆ –Š‡ •—•„‡” ‘ˆ „—‹Ž†‹•‰ „Ž‘…•• –Šƒ• –Š‡ ’”‹••ä ‹˜‡• –Šƒ– –Š‡ •‘•æˆŽ—‘”‹•ƒ–‡† •‘•‘•—…Ž‡ƒ” …‘•’Ž‡š Šƒ• •‘ ’”‡ˆ‡”‡•…‡ ˆ‘” IDF ‘” PHU ‰‡‘•‡–”›á ‡•–”‘’› •‹‰Š– „‡


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‹‰—”‡ `ä ”‘’‘”–‹‘• ‘ˆ ‡ƒ…Š •’‡…‹‡• ‘„•‡”˜‡† ˆ‘” ƒ –‡–”ƒŠ‡†”‘• _ ƒ•† „ –‡–”ƒ‰‘•ƒŽ ’”‹•• `ƒ …‘•’ƒ”‡† –‘ –Š‡ „‹•‘•‹ƒŽ •–ƒæ –‹•–‹…ƒŽ †‹•–”‹„—–‹‘•ä ””‘” „ƒ”• ”‡’”‡•‡•– –Š‡ •–ƒ•†ƒ”† †‡˜‹ƒ–‹‘•• ‘ˆ –Š‡ ƒ•‘—•–• ‘ˆ ‡ƒ…Š …‘•‰‡•‡” •‡ƒ•—”‡† „‡–™‡‡• –Š‡ †‹ˆæ ˆ‡”‡•– …Šƒ”‰‡ •–ƒ–‡• ‘„•‡”˜‡† ‹• –Š‡ æ ä … ƒ•† † ’”‘˜‹†‡ ’Ž‘–• ‘ˆ –Š‡ ‡•‡”‰› ‘ˆ ‡ƒ…Š •’‡…‹‡• ”‡Žƒ–‹˜‡ –‘ –‡–”ƒŠ‡†”‘• _ ‹• … á …‘•–ƒ‹•‹•‰ ‘•Ž› •‘•æˆŽ—‘”‹•ƒ–‡† ”‡•‹†—‡•á ƒ•† –Š‡ –‡–”ƒ‰‘•ƒŽ ’”‹•• `ƒ ‹• † á …‘•–ƒ‹•‹•‰ ‘•Ž› ˆŽ—‘”‹•ƒ–‡† ”‡•‹†—‡•ä ”– ƒ•† ”’ ”‡ˆ‡” –‘ –Š‡ ”‡Žƒ–‹˜‡ ‡•‡”‰‹‡• „‡–™‡‡• …‘•‰‡•‡”• ”‡•’‡…–‹˜‡Ž› ‹• –Š‡ …ƒ•‡• ‘ˆ –Š‡ –‡–”ƒŠ‡†”ƒŽ •‡”‹‡• ƒ•† –Š‡ ’”‹••ƒ–‹… •‡æ ”‹‡•ä D ”‡’”‡•‡•–• –Š‡ ‡•‡”‰‡–‹… †‡•–ƒ„‹Ž‹œƒ–‹‘• ’‡” Ž‹‰ƒ•† ‡š…Šƒ•‰‡†ä

†”‹˜‹•‰ –Š‡ ’”‡ˆ‡”‡•…‡ ‘ˆ –Š‡ •‘•æˆŽ—‘”‹•ƒ–‡† Ž‹‰ƒ•† –‘ ˆ‘”• –Š‡ –‡–”ƒŠ‡†”‘•ä Š‡ ‘„•‡”˜ƒ–‹‘• ‘ˆ –Š‡ Žƒ”‰‡” ’”‹•æ •ƒ–‹… •–”—…–—”‡• ˆ‘”•‡† ˆ”‘• ˆŽ—‘”‹•ƒ–‡† Ž‹‰ƒ•†• •—‰‰‡•–• –Šƒ– ’”‹••• ƒ”‡ ‡•–ŠƒŽ’‹…ƒŽŽ› ˆƒ˜‘”‡†á ‘—–™‡‹‰Š‹•‰ –Š‡ ‡•–”‘’‹… ’”‡ˆ‡”‡•…‡ –‘ ˆ‘”• –‡–”ƒŠ‡†”ƒä Š‡• –Š‡ •‡Žˆæƒ••‡•„Ž› ”‡ƒ…–‹‘• ™ƒ• ’‡”ˆ‘”•‡† —•‹•‰ ‡“—ƒŽ ƒ•‘—•–• ‘ˆ •—„…‘•’‘•‡•–• ƒ•† á –Š‡ •ƒ•‡ ”‡•—Ž– ™ƒ• ‘„–ƒ‹•‡† ƒ• ˆ‘” ™Š‡• –Š‡ ’”‡ˆ‘”•‡† …ƒ‰‡• ™‡”‡ •‹š‡† –‘‰‡–Š‡”á ‹•†‹…ƒ–‹•‰ –Šƒ– –Š‡ –Š‡”•‘†›•ƒ•‹… ’”‘†æ —…– †‹•–”‹„—–‹‘• ™ƒ• ƒ––ƒ‹•‡† ‹• „‘–Š …ƒ•‡•ä ‘”•ƒ–‹‘• ‘ˆ Žƒ”‰‡” ’”‹••ƒ–‹… •–”—…–—”‡•ä ‡–”ƒ‰‘•ƒŽ ’”‹•• `ƒ ™ƒ• –Š‡ ’”‡†‘•‹•ƒ•– •’‡…‹‡• ‘„–ƒ‹•‡† ‹• •‘Ž—æ –‹‘• ˆ”‘• –Š‡ •‡Žˆæƒ••‡•„Ž› ”‡ƒ…–‹‘• ‘ˆ †‹ƒŽ†‡Š›†‡ ™‹–Š ’æ•‡–Š‘š›ƒ•‹Ž‹•‡ ƒ•† ‡ b ^á ƒ• †‡–‡”•‹•‡† „› ] ä ‘–ƒ„Ž›á •‹‰•ƒŽ• ƒ––”‹„—–ƒ„Ž‡ –‘ ƒ ‡ ` b –‡–”ƒŠ‡†”ƒŽ …ƒ‰‡ ™‡”‡ ƒ„•‡•– ˆ”‘• –Š‡ ] •’‡…–”—•ä ‘™‡˜‡”á –Š‡ ‘„•‡”˜ƒ–‹‘• ‘ˆ •‹•‘” ’‡ƒ•• ‹•†‹…ƒ–‡† –Š‡ ’”‡•‡•…‡ ‘ˆ ƒ•‘–Š‡” †‹•…”‡–‡ •—’”ƒ•‘Ž‡…—Žƒ” •’‡…‹‡• ‹• •‘Ž—–‹‘•ä ‹˜‡• –Š‡ ’”‘’‡••‹–› ‘ˆ •—„…‘•’‘•‡•– –‘ ˆ‘”• •–”—…æ –—”‡• …‘•–ƒ‹•‹•‰ •‡” ˜‡”–‹…‡•á ™‡ Š›’‘–Š‡•‹œ‡† –Šƒ– –Š‡ ƒ††‹–‹‘•ƒŽ ] •‹‰•ƒŽ• •‹‰Š– „‡ †—‡ –‘ Š‹‰Š‡”æ‘”†‡” ’”‹••ƒ–‹… •–”—…–—”‡•ä Š‡ ‘’–‹•—• ’”‹•• •‹œ‡ …‘—Ž† „‡ –Š‡ ”‡•—Ž– ‘ˆ ƒ „ƒŽƒ•…‡ „‡–™‡‡• ‹•…”‡ƒ•‡† •–”ƒ‹• ‹• ••ƒŽŽ‡” •–”—…–—”‡• ƒ•† –Š‡ ‡•–”‘’‹… ’‡•ƒŽ–› ‘ˆ ˆ‘”•‹•‰ Žƒ”‰‡” •–”—…–—”‡•á ™‹–Š ˜ƒ”‹‘—• ˆƒ…–‘”• ƒ•† ‡ˆˆ‡…–• Šƒ˜‹•‰ –Š‡ ’‘–‡•–‹ƒŽ –‘ –‹’ –Š‹• „ƒŽƒ•…‡á ƒ• †‡•…”‹„‡† „‡Ž‘™ä

”‡˜‹‘—• ™‘”• Šƒ• •Š‘™• –Šƒ– …‘—•–‡”æƒ•‹‘•• …ƒ• ‹•ˆŽ—æ ‡•…‡ –Š‡ ’”‘†—…– †‹•–”‹„—–‹‘•• ‘ˆ •‡Žˆæƒ••‡•„Ž› ”‡ƒ…–‹‘•• †—‡ –‘ –Š‡‹” –‡•’Žƒ–‹•‰ ‡ˆˆ‡…–•ä^b ‡ ‹•ˆ‡””‡† –Šƒ– ƒ•‹‘• –‡•’Žƒ–‹‘• •‹‰Š– ’Žƒ› ƒ ”‘Ž‡ ‹• †‡–‡”•‹•‹•‰ –Š‡ ’”‡†‘æ •‹•ƒ•– ’”‘†—…–á „ƒ•‡† ‘• –Š‡ ‹•–‡”ƒ…–‹‘•• ‘„•‡”˜‡† „‡æ –™‡‡• –‡–”ƒ‰‘•ƒŽ ’”‹•• `ƒ ƒ•† bÇ „‘–Š ‹• •‘Ž—–‹‘• ƒ•† ‹• –Š‡ •‘Ž‹† •–ƒ–‡á ƒ• •‘–‡† ƒ„‘˜‡ä – Šƒ• ƒŽ•‘ „‡‡• •Š‘™• –Šƒ– –Š‡ ƒ•‹Ž‹•‡ •—„…‘•’‘•‡•– •ƒ› ‹•ˆŽ—‡•…‡ –Š‡ „‡Šƒæ ˜‹‘” ‘ˆ ƒ •–”—…–—”‡ ‹• •‘Ž—–‹‘•á †—‡ –‘ †‡Ž‘…ƒŽ‹œƒ–‹‘• ‘ˆ ‡Ž‡…–”‘• †‡••‹–› „‡–™‡‡• –Š‡ ƒ•‹Ž‹•‡ ”‡•‹†—‡ ƒ•† –Š‡ ”‡•– ‘ˆ –Š‡ Ž‹‰ƒ•†ä_\ ‹ˆˆ‡”‡•– …‘•„‹•ƒ–‹‘•• ‘ˆ ƒ•‹Ž‹•‡• ƒ•† …‘—•–‡” ƒ•‹‘•• ™‡”‡ –Š‡”‡ˆ‘”‡ •…”‡‡•‡† ‹• ‘”†‡” –‘ –ƒ”‰‡– –Š‡ Žƒ”‰‡” ’”‹••ƒ–‹… Š‘•‘Ž‘‰—‡• ‘ˆ `ä Š‡ •‡Žˆæƒ••‡•„Ž› ‘ˆ á ’æ–‡”–æ„—–›Žƒ•‹Ž‹•‡ ƒ•† ‹”‘• ’‡”…ŠŽ‘”ƒ–‡ ‰ƒ˜‡ ƒ •‹š–—”‡ ‘ˆ –™‘ •’‡…‹‡• ‹• –Š‡ ] •’‡…–”—•á „‘–Š Šƒ˜‹•‰ –Š”‡‡ †‹•–‹•…– Ž‹‰ƒ•† ‡•˜‹”‘•æ •‡•–•á …‘••‹•–‡•– ™‹–Š –Š‡ ’”‡•‡•…‡ ‘ˆ –™‘ ’”‹••ƒ–‹… •–”—…–—”‡•ä æ ’‡ƒ•• ™‡”‡ ‘„•‡”˜‡† …‘””‡•’‘•†‹•‰ –‘ „‘–Š ‡ d ]^ `„ ƒ•† ‡ ]\ ]a a„ •–”—…–—”‡• ‹‰—”‡ aƒ ä •–”‹‰—‹•‰Ž›á ™Š‡• ™ƒ• •‹š‡† ™‹–Š ’æ•‡–Š‘š›ƒ•‹Ž‹•‡ ƒ•† ‡ ˆ^ ^á –Š‡ ] •’‡…–”—• ƒ‰ƒ‹• ‹•†‹…ƒ–‡† –Š‡ ˆ‘”•ƒ–‹‘• ‘ˆ –™‘ ’”‡†‘•‹•ƒ•– •’‡…‹‡•â Š‘™‡˜‡”á ‹• …‘•æ –”ƒ•– –‘ –Š‡ ”‡•—Ž–• ™‹–Š ’æ–‡”–æ„—–›Žƒ•‹Ž‹•‡á æ ‰ƒ˜‡ ”‡•—Ž–• …‘••‹•–‡•– ™‹–Š –Š‡ ’”‡•‡•…‡ ‘ˆ „‘–Š ‡ ]\ ]a aƒ ƒ•† ‡ ]^ ]d •–”—…–—”‡• bƒ ‹‰—”‡ a„ ä ”›•–ƒŽ• ™‡”‡ ‘„–ƒ‹•‡† ˆ‘ŽŽ‘™‹•‰ •Ž‘™ ˜ƒ’‘” †‹ˆˆ—•‹‘• ‘ˆ „‡•œ‡•‡ ‹•–‘ –Š‡ •‹š–—”‡ ‘ˆ a… ƒ•† b…á ˆ‘”•‡† ˆ”‘• –Š‡ ”‡ƒ…–‹‘• ‘ˆ ™‹–Š ’æˆŽ—‘”‘ƒ•‹Ž‹•‡ ƒ•† ‡ ˆ^ ^ ‹•




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•–”ƒ‹•‡†á –Šƒ• –Š‡ Ž‹‰ƒ•†• ‘ˆ ’‡•–ƒ‰‘•ƒŽ aä ‘ •–ƒ–‹•–‹…ƒŽŽ› •‹‰•‹ˆ‹…ƒ•– †‹ˆˆ‡”‡•…‡• ‹• ‹•–‡”Ž‹‰ƒ•† UæU •–ƒ…•‹•‰ ™‡”‡ ‘„•‡”˜‡† „‡–™‡‡• –Š‡ •–”—…–—”‡• ‘ˆ `ƒ ƒ•† a…ä ‡•…‡á ’‡•–ƒ‰‘•ƒŽ ’”‹•• a •Š‘—Ž† „‡ ˆƒ˜‘”‡† ‘• ‡•–ŠƒŽ’‹… ‰”‘—•†•äaƒ ‡ –Š—• ‹•ˆ‡” –Šƒ– –Š‡ •–”‘•‰‡” •‡–ƒŽæŽ‹‰ƒ•† ‹•–‡”ƒ…–‹‘•• –Šƒ– ”‡•—Ž– ˆ”‘• –Š‡ ‹•…‘”’‘”ƒ–‹‘• ‘ˆ •‘”‡ ‡Ž‡…–”‘•æ”‹…Š ƒ•‹Ž‹•‡• ƒ”‡ •‡‡†‡† –‘ •–ƒ„‹Ž‹œ‡ –Š‡ •‘”‡ Š‹‰ŠŽ›æ•–”ƒ‹•‡† –‡–”ƒ‰‘•ƒŽ ’”‹••ƒ–‹… •–”—…–—”‡ `ä Š‡ •–”‡•‰–Š ‘ˆ –Š‡ •‡–ƒŽæŽ‹‰ƒ•† ‹•–‡”ƒ…–‹‘•á ƒ• ‹•ˆŽ—‡•…‡† „› –Š‡ •—„•–‹–—‡•–• ‘ˆ –Š‡ ƒ•‹Ž‹•‡ ”‡•‹†—‡•á –Š—• ‹•’ƒ…–• •–”‘•‰Ž› —’‘• –Š‡ ‡“—‹Ž‹„”‹—• „‡–™‡‡• –Š‡•‡ ’”‹••ƒ–‹… •–”—…–—”‡•ä

Ž–Š‘—‰Š ‰”‡ƒ– •–”‹†‡• Šƒ˜‡ „‡‡• •ƒ†‡ –‘™ƒ”†• –Š‡ ”ƒ–‹‘•ƒŽ †‡•‹‰• ‘ˆ •—’”ƒ•‘Ž‡…—Žƒ” •–”—…–—”‡• ‹• ”‡…‡•– ›‡ƒ”•á •ƒ•› •—„–Ž‡ ˆƒ…–‘”• ”‡“—‹”‡ ƒ ‰”‡ƒ–‡” †‡‰”‡‡ ‘ˆ —•†‡”•–ƒ•†‹•‰ „‡ˆ‘”‡ …‘•…‡’–• ‘ˆ ”‡–”‘•›•–Š‡–‹… ƒ•ƒŽ›•‹•_` …ƒ• „‡ ƒ• ”‡ƒ†‹Ž› ƒ’’Ž‹‡† –‘ –Š‡•‡ •‡–ƒŽæ‘”‰ƒ•‹… ƒ••‡•æ „Ž‹‡• ƒ• –‘ ’—”‡Ž› ‘”‰ƒ•‹… •‘Ž‡…—Ž‡•ä Š‹• ™‘”• ‡Ž—…‹†ƒ–‡• •‡› ˆƒ…–‘”• –Šƒ– Ž‡ƒ† ƒ „‹†‡•–ƒ–‡ Ž‹‰ƒ•† –‘ ˆ‘”• •‡” ”ƒ–Š‡” –Šƒ• ˆƒ… •‡–ƒŽ ˜‡”–‹…‡• ƒ •ƒŽ‹‡•– ˆ‡ƒ–—”‡ ‘ˆ •‘”‡ •–”—…–—æ ”ƒŽŽ› …‘•’Ž‡š ƒ••‡•„Ž‹‡• ™Š‹…Š •ƒ› ‹• –—”• Ž‡ƒ† –‘ •‘”‡ …‘•’Ž‡š ˆ—•…–‹‘••ä Š‡ ’”‹••ƒ–‹… •–”—…–—”‡• ˆ‘”•‡† •‡Ž‡…–‹˜‡Ž› †—”‹•‰ –Š‡ …‘—”•‡ ‘ˆ –Š‹• •–—†› •‹‰Š– ‡•„‡† ‹• •‡•„”ƒ•‡• ƒ•† ƒ…– ƒ• …Šƒ••‡Ž• –‘ ‰ƒ–‡ ’ƒ••ƒ‰‡ ‘ˆ ••ƒŽŽ •‘Ž‡…—Ž‡• ‘” ‹‘••ä_a ‘ ”‡ƒŽ‹œ‡ –Š‹• ’‘–‡•–‹ƒŽá „‘–Š …Šƒ••‡Ž ’‘”‡ •‹œ‡ ƒ•† …Šƒ••‡Ž Ž‡•‰–Š •—•– „‡ …‘•–”‘ŽŽ‡†ä Š‹• •–—†› ”‡’‘”–• –Š‡ •›•–Š‡•‹• ‘ˆ ‘•‡ ‘ˆ –Š‡ Žƒ”‰‡•– ’”‹••ƒ–‹… ƒ”…Š‹–‡…–—”‡• ’”‡’ƒ”‡† –‘ †ƒ–‡á ƒ•† ”‡˜‡ƒŽ• Š‘™ –Š‡ ”‡Žƒ–‹˜‡ ƒ•‘—•–• ‘ˆ –‡–”ƒ‰‘•ƒŽ ƒ•† ’‡•–ƒ‰‘•ƒŽ ’”‹••• …ƒ• „‡ “—ƒ•–‹–ƒ–‹˜‡Ž› …‘•–”‘ŽŽ‡† —•‹•‰ –Š‡ ƒ••‡–– ‡“—ƒæ –‹‘•ä ‡ Šƒ˜‡ ƒŽ•‘ “—ƒ•–‹ˆ‹‡† –Š‡ ‡•‡”‰‡–‹… ’”‡ˆ‡”‡•…‡ ‘ˆ ˆŽ—‘”‹•ƒ–‡† Ž‹‰ƒ•†• –‘ ˆ‘”• •‡” ˜‡”–‹…‡•á ƒ•† –Š‡”‡ˆ‘”‡ ’”‹••ƒ–‹… •–”—…–—”‡•á ˆ‹•†‹•‰ ‹– ‰”‡ƒ–‡” –Šƒ• –Š‡ ’”‡ˆ‡æ ”‡•…‡ ‘ˆ •‘•æˆŽ—‘”‹•ƒ–‡† Ž‹‰ƒ•†• –‘ ‰‡•‡”ƒ–‡ ˆƒ… ˜‡”–‹…‡• ƒ•† –Š—• –‡–”ƒŠ‡†”ƒä Š‡ ˆ‘”•ƒ–‹‘• ‘ˆ Žƒ”‰‡” Š‡šƒ‰‘•ƒŽ ’”‹••• …‘—Ž† ƒŽ•‘ „‡ ˆƒ˜‘”‡† –Š”‘—‰Š ˜ƒ”‹ƒ–‹‘• ‘ˆ –Š‡ …‘—•–‡” ƒ•‹‘•ä ‡ ƒ‹• •‡š– –‘ ‡š’Ž‘”‡ –Š‡ ˆ—•…–‹‘•• ‘ˆ –Š‡•‡ •‡™ •–”—…–—”‡•á ƒ•† –‘ ƒ’’Ž› –Š‡•‡ Ž‡••‘•• –‘ –Š‡ …‘••–”—…–‹‘• ‘ˆ ›‡– •‘”‡ •–”—…–—”ƒŽŽ› …‘•’Ž‡š •—’”ƒ•‘Ž‡æ …—Žƒ” ƒ”…Š‹–‡…–—”‡• ‹•…‘”’‘”ƒ–‹•‰ •‡” •–‡”‡‘…‡•–‡”•ä

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1RWHV Š‡ ƒ—–Š‘”• †‡…Žƒ”‡ •‘ …‘•’‡–‹•‰ ¤•ƒ•…‹ƒŽ ‹•–‡”‡•–ä

$&.12:/('*(0(17 Š‹• ’”‘Œ‡…– Šƒ• ”‡…‡‹˜‡† ˆ—•†‹•‰ ˆ”‘• –Š‡ —”‘’‡ƒ• •‹‘•=• ‘”‹œ‘• ^\^\ ”‡•‡ƒ”…Š ƒ•† ‹••‘˜ƒ–‹‘• ’”‘æ ‰”ƒ••‡ —•†‡” –Š‡ ƒ”‹‡ •Ž‘†‘™••ƒæ —”‹‡ ‰”ƒ•– ƒ‰”‡‡æ •‡•– ‘ b`^]e^ ƒ•† ™ƒ• •—’’‘”–‡† „› –Š‡ •‰‹•‡‡”æ ‹•‰ ƒ•† Š›•‹…ƒŽ …‹‡•…‡• ‡•‡ƒ”…Š ‘—•…‹Ž ä Š‡ ƒ—–Š‘”• –Šƒ•• ‹ƒ•‘•† ‹‰Š– ‘—”…‡ ˆ‘” •›•…Š”‘æ –”‘• „‡ƒ•–‹•‡ ‘• ]e d`b` ƒ•† ]]_ec á –Š‡ ‡æ ’ƒ”–•‡•– ‘ˆ Š‡•‹•–”› ˆƒ…‹Ž‹–›á •‹˜‡”•‹–› ‘ˆ ƒ•æ „”‹†‰‡á ƒ•† –Š‡ ƒ–‹‘•ƒŽ ƒ•• ’‡…–”‘•‡–”› ƒ…‹Ž‹–› ƒ– ™ƒ••‡ƒ •‹˜‡”•‹–›ä ä ä ƒ…••‘™Ž‡†‰‡• –Š‡ ƒ•„”‹†‰‡ ‘••‘•™‡ƒŽ–Šá —”‘’‡ƒ• ƒ•† •–‡”•ƒ–‹‘•ƒŽ ”—•– ƒ•† –Š‡ ”±†±”‹… ‘•–ƒ‹•‡ •…Š‘Žƒ”•Š‹’ ˆ”‘• ‹…Š‡æ Ž‹• ä ä ä ä ƒ…••‘™Ž‡†‰‡• –Š‡ ‡”…Š‡Ž •‹–Š ‡•‡ƒ”…Š ‡ŽŽ‘™•Š‹’ ˆ”‘• –Š‡ •‹˜‡”•‹–› ‘ˆ ƒ•„”‹†‰‡ ƒ•† ƒ ‡Žæ Ž‘™•Š‹’ ˆ”‘• ‘”’—• Š”‹•–‹ ‘ŽŽ‡‰‡á ƒ•„”‹†‰‡ä ä ä ä ƒ…••‘™Ž‡†‰‡• –Š‡ ƒ–‡• ƒ•„”‹†‰‡ ”—•– ˆ‘” Šä ä ˆ—•†æ ‹•‰ä

5()(5(1&(6 ƒ ›•‡á äæ äâ ‡˜‡•á ä äâ ‡‹‰Šá ä äâ … —”•‡›á ä äâ ‹••ƒ•‡•á äâ …Š—Ž–œá ä ƒ–ä Š‡•ä ^\]^á dá ]aæ^\â „ Š‹…Šƒ•á ä äâ ƒ•–”‹ŽŽá ä äâ ‡ƒ•‡á ä äâ Š‹—á äæ äâ ƒ˜‡á ä ä äâ –™‘‘†á ä äâ –‘††ƒ”–á ä ä …‹‡•…‡ ^\\`á c`dá ]_\dæ]_]^â … ‡˜‡•á ä äâ Ž‹‰Š–á ä äâ ƒ•’„‡ŽŽá ä äâ ‡‹‰Šá ä äâ … —”•‡›á ä ä •‰‡™ä Š‡•ä •–ä †ä ^\]]á e`á e^b\æe_^câ † ‘”‰ƒ•á ä äâ ƒ—˜ƒ‰‡á äæ äâ –‘††ƒ”–á ä ä Š‡•ä ‡˜ä ^\]]á aaaá a`_`æa`b`â ‡ ƒ”†á ä ä Š‡•ä ‘••—•ä ^\\eá ``dcæ`èeâ ˆ ƒ•“—ƒŽ‡á äâ ƒ––‹•á äâ •…—†‡”‘æ †ž•á ä äâ ƒ”–À•‡œæ ‡Ž•‘•–‡á äâ †‡ ‡•†‘œƒá ä ƒ–ä ‘••—•ä ^\]^á cá cdaâ ‰ —•á äâ ƒ•‰á äâ ‘—á äâ —ƒ•‰á äâ —á äâ ‹á äâ Š‡•á äæ äâ —á äâ ƒ˜‹•á ä äâ —á äâ ƒ•‰á äæ äâ ‹á ä ä •ä Š‡•ä ‘…ä ^\]aá acgá ]aabæ]ab`ä ^ ƒ ‡‹•”‹…Šá äâ ”ƒ—Ž•‡•á ä ä äâ ‘Žœ™‡„‡”á äâ ‹…Š–‡”á äâ —•œá äâ ƒ•–•‡”á ä äâ ”ƒ„„‡•„‘”‰á ä äâ —••‡••á äâ •‰‡”á ä ä äâ …ŠƒŽŽ‡›á ä ä ä •ä Š‡•ä ‘…ä ^\]aá acgá `_d^æ`_e\â „ ƒ—”‘á äâ Ž‹’”ƒ•†‹á äâ ‡’–‹ƒ†‹á äâ ‡Š”á ä äâ ‡ ‘Žƒá ä Š‡•ä ‘…ä ‡˜ä ^\]`á dcá `]``æ`]bbâ … ‘‘•á ä äâ —™ƒ„ƒ”ƒá äâ ‹•á äæ äâ ‹”•‹•á ä ä …‹‡•…‡ ^\]\á cc`á bbæbeâ † ‘‘•á ä äâ ƒŒ’ƒ›‡‡á äâ ‡‡á ä äâ –ƒ•‰á ä äâ Š‹á äæ ä ……ä Š‡•ä ‡•ä ^\]_á dfá ^`b`æ^`c`â ‡ ƒ—Ž••‡”á ä äâ ƒ•‡”á ä äâ „†ƒŽŽƒŠ ƒ•‡•á ä äâ Žƒ”••‘•á äâ ‘šá ä äâ —”•ƒ•‹á äâ ‘™•‘•á ä äâ Š‹ŽŽ‹’•á ä äâ ‘’‡”á ä äâ ‹•’•‘•á ä äâ …‘––á ä ƒ–ä Š‡•ä ^\]`á fá cecæd\_â ˆ Šƒ•á ä äæ äâ ƒ•á ä äâ ƒ•ƒ•ƒá äâ ‘•‰á ä äæ äâ ƒ•á ä äæ ä ”‘…ä ƒ–ä …ƒ†ä …‹ä ^\]aá aabá be\æbeaâ ‰ ƒ–—•á ä äâ —á äâ ’”ƒŠƒ•‹ƒ•á ä ……ä ]


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Š‡•ä ‡•ä ^\]`á dgá ^]`]æ^]èâ Š ‡‡á ä äâ ‘•‰á äâ ƒ”•á äâ ƒ‹•á äæ äâ ‡‡á ä ä •ä Š‡•ä ‘…ä ^\]\á acbá ]^]__æ]^]``â ‹ Šƒ•‰á äâ ‹•á ä äâ ‹•á äæ äâ Šƒ•‰á äâ ƒ••‡”á ä äâ ›•…Šá ä äâ ‘’‘˜á äâ ‹ŽŒƒ•‹©á ä eäâ ••Ž›•á ä äâ ‡••Ž‡”á ä ä ä •ä Š‡•ä ‘…ä ^\]aá acgá ccbeæccc`ä _ ƒ Šƒ•”ƒ„ƒ”–›á äâ —•Š‡”Œ‡‡á ä äâ –ƒ•‰á ä ä Š‡•ä ‡˜ä ^\]]á aaaá bd]\æbe]dâ „ —Œ‹–ƒá äâ ‘•‹•ƒ‰ƒá äâ ‘”‹á äâ Š‡””‹‡•á ä ……ä Š‡•ä ‡•ä ^\\aá chá _beæ_cdä ` ƒ ‹Ž„ƒ•á äâ ‹”–•…Š‹•á äâ …‘’‡ŽŽ‹–‹á äâ ‡˜‡”‹•á ä Š‡•ä …‹ä ^\]^á cá c\]æc\`â „ —œ—•‹á äâ ƒ™ƒ•‘á äâ —Œ‹–ƒá ä •‰‡™ä Š‡•ä •–ä †ä ^\\cá dfá ^d]eæ^d^^â … ƒ””ƒá äâ Ž‡‰‰á ä äâ ‹–•…Š•‡á ä ä •‰‡™ä Š‡•ä •–ä †ä ^\]_á ebá `d_cæ`d`\ä a ƒ ‡‹Žƒ•†–á äâ ”‘ˆˆá ä äâ ƒš‡ŽŽá äâ ‹••ƒ•‡•á äâ …ŠƒŽŽ‡›á ä ä •‘”‰ä Š‡•ä ^\\dá dgá caddæcaedâ „ ”ƒ—•á äâ —†³æÀ•••ýá äâ ˜ƒ«•ƒá äâ ƒ—˜ƒ‰‡á äæ ä •‰‡™ä Š‡•ä •–ä †ä ^\\bá deá âdæ^b]â … ƒ•ƒ•‘–‘á äâ ”‹ˆá ä äâ –ƒ•‰á ä ä ä •ä Š‡•ä ‘…ä ^\\_á abeá ]^_\eæ]^_]câ † —á äæ äâ ‡‡á äæ äâ ‡á äæ äâ Šƒ•á äæ ä •‰‡™ä Š‡•ä •–ä †ä ^\]aá edá b^_]æ b^_aâ ‡ —Œ‹–ƒá äâ ƒ•ƒ•‹á äâ ‹–•—Šƒ•Š‹á äâ —Œ‹–ƒá äâ ƒœƒ•‹á äâ ƒ•ƒ‰—…Š‹á äâ ‰—”ƒá ä Š‡•ä ‘••—•ä ]eebá ]a_aæ]a_bä b ƒ —•á äæ äâ ƒ–‘á äâ —Œ‹–ƒá ä ƒ–ä Š‡•ä ^\]^á dá __\æ___â „ ‹•Š‹á äâ •‹–ƒá äâ ‘•Š‹œƒ™ƒá ä •‰‡™ä Š‡•ä •–ä †ä ^\]`á ecá _b\`æ_b\câ … ƒ”•‡•á ä äâ ‘ŽŽ‹••á ä äâ ‘Š••‘•á ä ä Š‡•ä ‘…ä ‡˜ä ^\]`á dcá ]dâæ]d_`ä c ƒ ”‡›‡á äâ ‹…Š‡Žá äâ –ƒŽ•‡á äâ ƒ™Ž‹…œ‡•á äâ ”ƒ—‡•†‘”ˆá äâ Ž‡˜‡”á ä ä ä •ä Š‡•ä ‘…ä ^\]_á aceá d`cbæd`ceâ „ …Š‡”‡”á äâ ƒ—Ž†‡”á ä äâ ‘Š••‘•á ä äâ ƒ›•‘•†á ä ä •‰‡™ä Š‡•ä •–ä †ä ]eeeá chá ]adcæ]ae^â … ‡•‰á äâ ‹á äâ —á äâ Š‘—á äæ äâ ‰á ä ä •‘”‰ä Š‡•ä ^\\bá deá `\_aæ`\`bâ † —•–‡Ž…‡ƒ•á ä Š‡•ä ‘…ä ‡˜ä ^\]`á dcá ]d]_æ]d^`ä d ƒ ƒ•á äâ —á äæ äâ ‘‘•á ä äâ —ƒ•‰á äâ ƒ•‰á äæ äâ —•‰á äæ äâ –ƒ•‰á ä ä ”‘…ä ƒ–ä …ƒ†ä …‹ä ^\]`á aaaá dc]cædc^^â „ ƒ•á äâ ‹…Š‡Žá äâ ‡á äâ Š‡•á äæ äâ –ƒŽ•‡á äâ ‘Š•á äâ Ž‡˜‡”á ä ä •‰‡™ä Š‡•ä •–ä †ä ^\]_á ebá ]_]eæ]_^_â … ƒ•ƒ•Š‹–ƒá äæ‹äâ ƒ™ƒ•‘á äâ —Œ‹–ƒá ä ä •ä Š‡•ä ‘…ä ^\\cá abiá ]da\æ]da]â † ‹•Š‹á äâ •‹–ƒá äâ ƒ•‹›ƒá äâ ƒ›ƒ•Š‹á äâ •—á äæ äâ ‘•Š‹œƒ™ƒá ä ä •ä Š‡•ä ‘…ä ^\]_á aceá ]êcbæ]êceä e ƒ•‰á äâ ƒ•‰á äæ äâ ƒ•‰á äæ ä Š‡•ä ‘…ä ‡˜ä ^\]bä ]\ ƒ ‹á äâ ”‡‰ƒá äâ ƒ’–ƒ‹•á äâ ƒ‹ˆ‡”á ä ä Š‡•ä ‘••—•ä ^\]^á dhá ]\êaæ]\êcâ „ ƒŠƒ–ƒá äâ ”‹•…Š•ƒ••á ä äâ ò”–Š•‡”á ä ä •ä Š‡•ä ‘…ä ^\]_á aceá ]ababæ]abb]â … —•–‡Ž…‡ƒ•á äâ ‘••‡•‡•á ä äâ —•…ƒ•á ä äâ Šƒ•‰á äâ ƒ–•‘•á ä äâ ƒ• ‡”•‡Žá äâ ƒ”•‘•á ä äâ ƒ›á ä ä ä •ä Š‡•ä ‘…ä ^\]^á acdá daâæda_`â † ƒ•á äæ äâ ƒ•á äæ äâ Šƒ•‰á äæ äâ Š‘—á äæ äâ ò•œŽ‹á äæ äâ —•á äæ ä ä •ä Š‡•ä ‘…ä ^\]aá acgá daa\ædaaaâ ‡ Ž„”‡…Š–á äâ Šƒ•‰á äâ

Š›••‡•á äâ –—„‡•”ƒ—…Šá äâ ‹••Ž‡”á ä ä äâ …ŠƒŽŽ‡›á ä ä —”ä ä ”‰ä Š‡•ä ^\]^á bàbá ^`^^æ^`^câ ˆ ‡•á äæ äâ ‹—á äâ ƒ•‰á äæ äâ ‹á äâ —á äæ ä Š‡•ä ‘••—•ä ^\]aá eaá cddæce]â ‰ ‹•‰á äâ ‡á äâ ƒ•‰á äâ —ƒ•á ä ä •ä Š‡•ä ‘…ä ^\]aá acgá _ebcæ _ec`â Š ƒ•‰á äæ äâ ƒ›á ä äâ ‘™•ƒ•æ ƒ•‡•á ä •‰‡™ä Š‡•ä •–ä †ä ^\]^á eaá ^]]eæ^]^_ä ]] ƒ ‹†•ƒ”•Šá ä äâ ƒ—•–á ä äâ †ƒ••á äâ ƒ”†‹•‰á ä äâ —••‘á äâ Ž‡‰‰á äâ ƒ”†á ä ä ä •ä Š‡•ä ‘…ä ^\\dá ac`á ]a]bcæ]a]caâ „ ƒ••ƒ›á ä äâ œ…œ›’‹Ñ••‹á ä äâ ‡‹•••ƒ•á äâ ‘••‘•á ä äâ •—Ž†‡”•á ä ä äâ ›„–…Š‹•••‹á äâ ‹–•…Š•‡á ä ä •‰‡™ä Š‡•ä •–ä †ä ^\]aá edá ab_bæab`\â … Š‘—á äæ äâ ‹—á äâ Šƒ•á äæ äâ ƒ•‰á äæ äâ ‹á äâ ‰á äæ äâ —•á ä äæ äâ Š‡á äæ ä ä •ä Š‡•ä ‘…ä ^\]^á acdá d\`^æd\àä ]^ ‡ŽŽá ä äâ ‡ˆˆ‡”›á ä äâ … Ž‡˜‡”–›á ä äâ ƒ”†á ä ä •‰‡™ä Š‡•ä •–ä †ä ^\\^á daá â]aæâ]dä ]_ ‘•‹•ƒ‰ƒá äâ —œ—•‹á äâ —”ƒ•‡á äâ —Œ‹–ƒá ä ä •ä Š‡•ä ‘…ä ^\\aá abgá ]]ea\æ]]ea]ä ]` —•á äæ äâ ™ƒ•ƒá äâ ‰ƒ™ƒá äâ •Š‹†‘á äâ ƒ–‘á äâ œ‡•‹á äâ ‡‹á äâ ƒ•ƒ‰—…Š‹á äâ —Œ‹–ƒá ä …‹‡•…‡ ^\]\á cbhá ]]``æ]]`cä ]a ƒ —Œ‹–ƒá äâ ƒ‰ƒ‘á äâ ‰—”ƒá ä ä •ä Š‡•ä ‘…ä ]eeaá aagá ]bèæ]ba\â „ Šƒ•á äæ äâ ‹—á äæ äâ ™‘•‰á äæ ä •‘”‰ä Š‡•ä ^\]_á ebá ab`dæaba\â … ”Šƒ•á äâ ƒ”…‹á äâ Š‡””‹‡•á ä •‘”‰ä Š‹•ä …–ƒ ^\]aá dchá aæeä ]b ‡•–•…Šá ä äâ –‡‹•á äâ ‡‹•”‡‹…Šá äâ †‡„‹•á ä ä Š›•‹‘Žä ‡˜ä ^\\^á hbá a\_æabdä ]c ƒ ƒ•ƒ‹á äâ ƒ–‹Ž‡á ä ƒ•‰•—‹” ^\]_á biá e\_]æe\`\â „ ƒ”‰ƒ• ‡•–œ•…Šá äâ ‡••‹‰á äâ ƒ”‡†ƒá äâ ƒ–‹Ž‡á ä ……ä Š‡•ä ‡•ä ^\]_á dfá ^ce]æ^d\\â … ƒ›•‡•á ä ä äâ ƒŽ‡á ä ä Š‡•ä ‘••—•ä ^\]]á dgá d^\_æd^\eä ]d ä ƒ—Ž†‡”á äâ ä ƒ›•‘•†á ä ä Š‡•ä ‘…äá ƒŽ–‘• ”ƒ••ä ]eeeá ]]daæ]^\\ä ]e ‘••‘•á ä äâ ƒ””ƒá äâ Žƒ…•á ä äâ ‹–•…Š•‡á ä ä Š‡•ä ‘••—•ä ^\]_á diá ^`cbæ^è\ä ^\ ‹††‡ŽŽá ä äâ •—Ž†‡”•á ä ä äâ Ž‡‰‰á ä äâ ”‹•–‘˜ƒá ä äâ ”‡‹•‡”á äâ Š‘„—”•á ä äâ ‹–•…Š•‡á ä ä ƒ–ä Š‡•ä ^\]^á dá ca]æcabä ^] ƒ„„á ä äâ Ž‡–…Š‡”á ä ä ƒŽ–‘• ”ƒ••ä ^\]aá ddá ``\bæ``^^ä ^^ ƒ ƒá äâ •—Ž†‡”•á ä ä äâ ”‹•–‘˜ƒá ä äâ Ž‡‰‰á ä äâ ‘••‘•á ä äâ ƒ””ƒá äâ ‹–•…Š•‡á ä ä ä •ä Š‡•ä ‘…ä ^\]_á aceá abcdæabd`â „ —•ƒ•ƒá äâ Ž‡‰‰á ä äâ ‹–•…Š•‡á ä ä •‰‡™ä Š‡•ä •–ä †ä ^\]^á eaá ]`b`æ]`bdä ^_ ‡•‰á äâ Ž‡‰‰á ä äâ Š‘„—”•á ä äâ ‹–•…Š•‡á ä ä ä •ä Š‡•ä ‘…ä ^\]]á accá ]_ba^æ]_bb\ä ^` ƒ ƒ—Ž‹•‰á ä ä •ä Š‡•ä ‘…ä ]e_]á ecá ]_bcæ ]`\\â „ ‘•†‹á ä ä Š›•ä Š‡•ä ]eb`á fhá ``]æà]ä â ƒ•’„‡ŽŽá ä äâ ‹–•…Š•‡á ä ä ›•Ž‡–– ^\\dá b``há _\ccæ_\e\ä



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^b ‹††‡ŽŽá ä äâ ”‹•–‘˜ƒá ä äâ Ž‡‰‰á ä äâ ‘‘†á ä äâ ”‡‹•‡”á äâ ‹–•…Š•‡á ä ä ä •ä Š‡•ä ‘…ä ^\]_á aceá ^c^_æ^c__ä ^c ƒ Š‹ˆ‘–‹†‡•á ä äâ ‹Ž‡•á ä äâ —•„ƒ”á ä ä ä •ä Š‡•ä ‘…ä ^\]_á aceá _\_eâ „ Š‹ˆ‘–‹†‡•á ä äâ —•„ƒ”á ä ä ……ä Š‡•ä ‡•ä ^\]_á dfá de`æe\bä ^d ƒ ”ƒ••á äâ ”ƒ—•‡á äâ ‡”„•–æ ”•‡”á äâ –ƒŽ•‡á äâ Ž‡˜‡”á ä ä ƒŽ–‘• ”ƒ••ä ^\]`á dcá àdcæ àe^â „ •‘™••ƒá äâ ‹ŽŒƒ•‹©á ä eä ä •ä Š‡•ä ‘…ä ^\]]á accá c^`æc^câ … Š‡•‰á äæ äâ ƒ•‰á äæ äâ ‘”–Š”‘’á ä äâ Š‘•Šá äâ –ƒ•‰á ä ä •‘”‰ä Š‡•ä ^\\dá dgá `c\bæ`c]]â † —á äâ •ƒƒ…•á ä ä •ä Š‡•ä ‘…ä ^\\_á abeá `d_]æ`d_aä ê Žƒ…•á ä äâ ‘‘†á ä äâ …Š™ƒ”œá ä äâ ‘••‘•á ä äâ ‘Ž•–‡‹•á ä äâ –‡ˆƒ••‹‡™‹…œá ä äâ …ŠƒŽŽ‡›á ä äâ ƒ•†‡”•á ä ä äâ ‹–•…Š•‡á ä ä Š‡•ä …‹ä ^\]bá gá ^b]`æ^b^\ä _\ ‘„‡”–•á ä äâ ‹Ž‰”‹•á ä äâ ‘‘’‡”á ä äâ ‘••‘•á ä äâ ƒ””ƒá äâ ‹–•…Š•‡á ä ä ä •ä Š‡•ä ‘…ä ^\]aá acgá ]\\bdæ]\\c]ä

_] ƒ ƒ…‘—”á äâ ‹•‰Ž‹•‰‡”á äâ ƒ˜ƒ”‰‡”á äâ ‘”…Š‡æ ƒŽ†‹•ƒ••á ä Š‡•ä ‘••—•ä ]eecá ^^daæ ^^dbâ „ ƒ…‘—”á äâ ‘”ƒŽ‡†ƒá ä Š‡•ä ‘••—•ä ^\\eá c\c_æc\deä _^ ƒ ‡‡Žƒ•ƒ•†ƒ•á ä äâ ‹•±•‡œá äâ Š‘„—”•á ä äâ ‹–•…Š•‡á ä ä •‰‡™ä Š‡•ä •–ä †ä ^\]aá edá ]`_cdæ]`_d^â „ ”‹•–‘˜ƒá ä äâ •—Ž†‡”•á ä ä äâ Ž‡‰‰á ä äâ ”‡‹•‡”á äâ ‹–•…Š•‡á ä ä Š‡•ä …‹ä ^\]]á bá b_dæb`]ä __ ƒ ƒ••‡––á ä ä Š‡•ä ‡˜ä ]e_aá agá ]âæ]_bâ „ ƒ••…Šá äâ ‡‘á äâ ƒˆ–á ä ä Š‡•ä ‡˜ä ]ee]á iaá ]baæ]eaä _` ‘”‡›á ä ä Š‡•ä ‘…ä ‡˜ä ]eddá agá ]]]æ]__ä _a ƒ—†”›á äâ ‘ŽŽ‘–á äâ ‘”–‡ƒ—á äâ ‹–˜‹•…Š—•á äâ ƒ”‡†ƒá äâ ‹•Š‹Šƒ”ƒá äâ ƒ•‹•‹á äâ ‡””‡–á äâ ‘•ƒ•á äâ ƒ•ƒ‹á äâ ŠƒŠá ä äâ ‘•á äâ ‘”†±á äâ ƒŽ—•†ƒ”á äâ ”ƒ•á ä äâ ƒ–‹Ž‡á ä †˜ä —•…–ä ƒ–‡”ä ^\\bá afá ]beæ]ceä


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Figure 1. Self-assembly of fac and mer mononuclear complexes 1 and 2. 1H NMR spectra (400 MHz, 298 K, CD3CN) of the imine regions of 1 and 2. Self-assembly of tetrahedral 3 and tetragonal prismatic 4 from the non-fluorinated C and tetrafluorinated D subcomponents respectively. 369x232mm (192 x 192 DPI)


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Figure 2. Views of the single crystal X-ray structure of 4a (a) showing the top and bottom rings linked by axial ligands, with linkages between FeII centers (purple spheres) added in order to highlight the D4 point symmetry; (b) showing the ligands in a space-filling view down the central channel; (c) highlighting a pair of mer vertices, with the three magnetically distinct environments shown in blue, red, and green; (d) showing the placement of the ordered PF6− counterions above the -C6F4- rings. In all views the non-encapsulated anions, solvent molecules and disorder are omitted for clarity. 564x565mm (192 x 192 DPI)



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Figure 3. ESI-MS of a mixture of preformed structures 3 and 4a in a 2:1 ratio after equilibration at 50 °C for one week. 604x594mm (192 x 192 DPI)


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Figure 4. Proportion of each species observed for (a) tetrahedron 3 and (b) tetragonal prism 4a compared to the binomial (statistical) distribution. Error bars represent the standard deviations of the amounts of each congener measured between the different charge states observed in the ESI-MS. (c) and (d) provide plots of the energy of each species relative to tetrahedron 3 in (c), containing only non-fluorinated C residues, and the tetragonal prism 4a in (d), containing only fluorinated D residues. Ert and Erp refer to the relative energies between congeners respectively in the cases of the tetrahedral series and the prismatic series. α represents the energetic destabilization per ligand exchanged. 393x262mm (192 x 192 DPI)



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Figure 5. ESI-MS of a mixture of (a) 4b and 5b and (b) 5a and 6a. 654x1034mm (192 x 192 DPI)


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Figure 6. Single crystal X-ray structure of 5c showing (a) the two pentagonal faces linked by axial ligands, with connections between metal centers (purple spheres) added to highlight the C5h point symmetry; (b) spacefilling view down the central channel; (c) side view showing the specific positions of the localized PF6− counterions. In all views the non-encapsulated anions, solvent molecules and disorder are omitted for clarity. 793x261mm (192 x 192 DPI)



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Figure 7. (a) MM3-optimized molecular model of hexagonal prism 6h (R=H). Connections between metal centers (purple spheres) have been added to highlight the D6 point symmetry; (b) spacefilling view down the central channel. No anions were modeled. 327x594mm (192 x 192 DPI)


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Figure 8. Equilibria between 4 and 5 show a linear free energy relationship between log(K) and σp+, following the Hammett Equation. The error bars show standard deviations of log(K) over 5 runs. 593x594mm (192 x 192 DPI)



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793x393mm (192 x 192 DPI)


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Perfluorinated Ligands Induce Meridional Metal ... - ACS Publications

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