Self-Healing Heterometallic Supramolecular Polymers Constructed by Hierarchical Assembly of Triply Orthogonal Interactions with Tunable Photophysical Properties

Article abstract of DOI:10.1021/jacs.9b09671

Here, we present a method for the building of new bicyclic heterometallic cross-linked supramolecular polymers by hierarchical unification of three types of orthogonal noncovalent interactions, including platinum(II)-pyridine coordination-driven self-asse

Full text of DOI:10.1021/jacs.9b09671

Subscriber access provided by Bibliothèque de l'Université Paris-Sud
Article
Self-Healing Heterometallic Supramolecular Polymers
Constructed by Hierarchical Assembly of Triply Orthogonal
Interactions with Tunable Photophysical Properties
Qian Zhang, Danting Tang, Jinjin Zhang, Ruidong Ni, Luonan Xu, Tian He,
Xiongjie Lin, Xiaopeng Li, huayu qiu, Shouchun Yin, and Peter J. Stang
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.9b09671 • Publication Date (Web): 16 Oct 2019
Downloaded from pubs.acs.org on October 20, 2019
Just Accepted
“Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted
online prior to technical editing, formatting for publication and author proofing. The American Chemical
Society provides “Just Accepted” as a service to the research community to expedite the dissemination
of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in
full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully
peer reviewed, but should not be considered the official version of record. They are citable by the
Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore,
the “Just Accepted” Web site may not include all articles that will be published in the journal. After
a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web
site and published as an ASAP article. Note that technical editing may introduce minor changes
to the manuscript text and/or graphics which could affect content, and all legal disclaimers and
ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or
consequences arising from the use of information contained in these “Just Accepted” manuscripts.
is published by the American Chemical Society. 1155 Sixteenth Street N.W.,
Washington, DC 20036
Published by American Chemical Society. Copyright © American Chemical Society.
However, no copyright claim is made to original U.S. Government works, or works
produced by employees of any Commonwealth realm Crown government in the course
of their duties.

Page 1 of 19
Journal of the American Chemical Society
1
2
3
4
5
6
7
8
9
!
"#$%!&"'()ꢀ%!*!+,-!*&""'.ꢀ /0+&-,"!./"&+ꢀ1,"2-!+3ꢀ4,(3*+/.*!5ꢀ
62ꢀ%'!+&+.7'.&"ꢀA33!-6"2ꢀ,#ꢀ8+'0"2ꢀ9+*7,),(&"ꢀ:(*!+&.*',(3ꢀ;'*7ꢀ
8
/(&6"!ꢀ17,*,0723'.&"ꢀ1+,0!+*'!3
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
"#ꢀ$%"#&'(')'*ꢀ+"#,!#&ꢀ-"#&' ꢀ.!#/!#ꢀ$%"#&'ꢀ01!23#&ꢀ4!'ꢀ613#"#ꢀ71'ꢀ-!"#ꢀ89'ꢀ
('*
(
5
(
(
!
(
5
(
?'(
?')
7!3#&/!9ꢀ6!#'ꢀ7!"3:9#&ꢀ6!'ꢀ81";1ꢀ !1'ꢀ<%31=%1#ꢀ>!#' ꢀ@9,9Aꢀ.Bꢀ<,"#&
(C3DD9&9ꢀ3EꢀF",9A!"DG'ꢀC%9H!G,A;ꢀ"#2ꢀC%9H!="DꢀI#&!#99A!#&'ꢀ8"#&J%31ꢀ43AH"Dꢀ
K#!L9AG!,;'ꢀ8"#&J%31ꢀMNOOMP'ꢀ@Bꢀ0BꢀC%!#"Bꢀ
)+
"T9ꢀC!,;'ꢀK,"%ꢀURNNS'ꢀK#!,92ꢀ<,",9GB
5+9:"A,H9#,ꢀ3EꢀC%9H!G,A;'ꢀK#!L9AG!,;ꢀ3Eꢀ<31,%ꢀVD3A!2"'ꢀRSOSꢀI"G,ꢀV3WD9AꢀꢁL9#19'ꢀ
"H:"'ꢀVD3A!2"ꢀMMPSO'ꢀK#!,92ꢀ<,",9GB
9:"A,H9#,ꢀ3EꢀC%9H!G,A;'ꢀK#!L9AG!,;ꢀ3EꢀK,"%'ꢀMNQꢀ<31,%ꢀNROOꢀI"G,'ꢀ033HꢀSOSO'ꢀ<"D,ꢀ
6
-
A< 8=A48ꢀ
8
9A9ꢀW9ꢀ:A9G9#,ꢀ"ꢀH9,%32ꢀE3Aꢀ,%9ꢀX1!D2!#&ꢀ3Eꢀ#9WꢀX!=;=D!=ꢀ%9,9A3H9,"DD!=ꢀ=A3GGYD!#T92ꢀ
G1:A"H3D9=1D"Aꢀ:3D;H9AGꢀX;ꢀ%!9A"A=%!="Dꢀ1#!E!=",!3#ꢀ3Eꢀ,%A99ꢀ,;:9Gꢀ3Eꢀ3A,%3&3#"Dꢀ
3#=3L"D9#,ꢀ !#,9A"=,!3#G'ꢀ !#=D12!#&ꢀ :D",!#1HZ[[\Y:;A!2!#9ꢀ =33A2!#",!3#Y2A!L9#ꢀ
G9DEY"GG9HXD;'ꢀ J!#=Y,9A:;A!2!#9ꢀ =3H:D9]ꢀ "#2ꢀ %3G,^&19G,ꢀ !#,9A"=,!3#GBꢀ -%9ꢀ
D",!#1HY:;A!2!#9ꢀ=33A2!#",!3#ꢀ:A3L!29Gꢀ,%9ꢀ:A!H"A;ꢀ2A!L!#&ꢀE3A=9ꢀ,3ꢀE3AHꢀ2!G=A9,9ꢀ
A%3HX3!2"DꢀH9,"DD"=;=D9GBꢀ-%9ꢀ"GG9HXD;ꢀ239G#_,ꢀ!#,9AE9A9ꢀW!,%ꢀ,%9ꢀJ!#=Y,9A:;A!2!#9ꢀ
#
:
=
"
=
3H:D9]9G'ꢀW%!=%ꢀD!#Tꢀ,%9ꢀ2!G=A9,9ꢀH9,"DD"=;=D9Gꢀ!#,3ꢀD!#9"AꢀG1:A"H3D9=1D"Aꢀ:3D;H9AG'ꢀ
#2ꢀ,%9ꢀ=3#/1&",!3#ꢀD9#&,%ꢀ!Gꢀ9],9#292ꢀ1:3#ꢀ,%9ꢀE3AH",!3#ꢀ3Eꢀ,%9ꢀJ!#=Y,9A:;A!2!#9ꢀ
3H:D9]9G'ꢀW%!=%ꢀA92G%!E,Gꢀ,%9ꢀ"XG3A:,!3#ꢀ"#2ꢀ9H!GG!3#ꢀG:9=,A"BꢀV!#"DD;'ꢀ%3G,Y&19G,ꢀ
!#,9A"=,!3#GꢀL!"ꢀX!GY"HH3#!1HꢀG"D,ꢀX!#2!#&ꢀ,3ꢀ,%9ꢀX9#J3YSNY=A3W#Y`ꢀZaSNC`\ꢀ&A31:Gꢀ
#ꢀ,%9ꢀ:D",!#1Hꢀ"==9:,3AGꢀ"EE3A2ꢀ,%9ꢀ=A3GGYD!#T92ꢀG1:A"H3D9=1D"Aꢀ:3D;H9AGBꢀa;ꢀ
3#,!#131Gꢀ!#=A9"G9ꢀ3Eꢀ,%9ꢀ=3#=9#,A",!3#ꢀ3Eꢀ,%9ꢀG1:A"H3D9=1D"Aꢀ:3D;H9Aꢀ,3ꢀ"ꢀA9D",!L9D;ꢀ
3
=
%
:
!&%ꢀD9L9D'ꢀG1:A"H3D9=1D"Aꢀ:3D;H9Aꢀ&9Dꢀ!Gꢀ3X,"!#92'ꢀW%!=%ꢀ9]%!X!,GꢀG9DEY%9"D!#&ꢀ
A3:9A,!9Gꢀ"#2ꢀA9L9AG!XD9ꢀ&9DbG3Dꢀ,A"#G!,!3#GꢀG,!H1D",92ꢀX;ꢀL"A!31Gꢀ9],9A#"DꢀG,!H1D!'ꢀ
dꢀ
!
#=D12!#&ꢀ,9H:9A",1A9'ꢀc "#2ꢀ=;=D9#BꢀF3A93L9A'ꢀ,%9ꢀ:%3,3:%;G!="Dꢀ:A3:9A,!9Gꢀ3Eꢀ,%9ꢀ
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 2 of 19
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
G1:A"H3D9=1D"Aꢀ:3D;H9AGꢀ=31D2ꢀX9ꢀ9EE9=,!L9D;ꢀ,1#92ꢀX;ꢀL"A;!#&ꢀ,%9ꢀG1XG,!,19#,Gꢀ3Eꢀ,%9ꢀ
:
A9=1AG3AꢀD!&"#2GB
:>8=9?@48:9>
N
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
<1:A"H3D9=1D"Aꢀ:3D;H9AG'ꢀ!B9Bꢀ:3D;H9A!=ꢀ"AA";Gꢀ3EꢀH3#3H9Aꢀ1#!,Gꢀ,%",ꢀ"A9ꢀ
"GG9HXD92ꢀX;ꢀA9L9AG!XD9ꢀ"#2ꢀ%!&%D;ꢀ2!A9=,!3#"Dꢀ#3#=3L"D9#,ꢀX3#2G'ꢀ%"L9ꢀ&"!#92ꢀ
A9H"AT"XD9ꢀ",,9#,!3#ꢀ219ꢀ,3ꢀ,%9ꢀ=3HX!#",!3#ꢀ3Eꢀ,%9ꢀ=3#L9#,!3#"Dꢀ:3D;H9A!=ꢀ:A3:9A,!9Gꢀ
"
#2ꢀ,%9ꢀE"G=!#",!#&ꢀE9",1A9GꢀD!T9ꢀG,!H1D!YA9G:3#G!L9ꢀ"#2ꢀG9DEY%9"D!#&ꢀ=":"X!D!,!9GBSYeꢀ
%9ꢀ2;#"H!=ꢀ:A3:9A,!9Gꢀ3Eꢀ,%9G9ꢀH",9A!"DGꢀ29A!L!#&ꢀEA3Hꢀ,%9ꢀA9L9AG!XD9ꢀ#3#=3L"D9#,ꢀ
-
X3#2GꢀH"T9ꢀG1:A"H3D9=1D"Aꢀ:3D;H9AGꢀ",,A"=,!L9ꢀE3AꢀL"A!31Gꢀ"::D!=",!3#G'ꢀG1=%ꢀ"Gꢀ2A1&ꢀ
29D!L9A;'ꢀX!3G9#G3AG'ꢀ,!GG19ꢀ9#&!#99A!#&'ꢀ3:,!="Dꢀ29L!=9G'ꢀ"=,1",3AGꢀ"#2ꢀ=3",!#&Gꢀ"#2ꢀ
,9],!D9GBNOYNQ
H3#&ꢀ ,%9ꢀ H!G=9DD"#931Gꢀ #3#=3L"D9#,ꢀ !#,9A"=,!3#G'ꢀ G1=%ꢀ "Gꢀ H9,"DYD!&"#2ꢀ
33A2!#",!3#'ꢀ%3G,Y&19G,ꢀ!#,9A"=,!3#G'ꢀ8YX3#2!#&'ꢀfYfꢀG,"=T!#&'ꢀL"#ꢀ29Aꢀg""DGꢀE3A=9G'ꢀ
;2A3:%3X!=ꢀE3A=9G'ꢀ9,='ꢀH9,"DYD!&"#2ꢀ=33A2!#",!3#ꢀ!Gꢀ3Eꢀ:"A,!=1D"Aꢀ!#,9A9G,ꢀ219ꢀ,3ꢀ!,Gꢀ
ꢀ
ꢁ
=
%
%
!&%ꢀ2!A9=,!3#"D!,;ꢀ"#2ꢀG,A3#&ꢀG,A9#&,%ꢀ"::A3"=%!#&ꢀ,%",ꢀ3Eꢀ=3L"D9#,ꢀX3#2GBNPYNU
ꢀ
F9,"DYD!&"#2ꢀ=33A2!#",!3#ꢀ%"GꢀX99#ꢀ29H3#G,A",92ꢀ,3ꢀX9ꢀ"#ꢀ9EE!=!9#,ꢀG,A",9&;ꢀE3Aꢀ
:A9:"A!#&ꢀG1:A"H3D9=1D"Aꢀ:3D;H9AGꢀG!#=9ꢀ!,ꢀ"DD3WGꢀ,%9ꢀ=3#G,A1=,!3#ꢀ3EꢀW9DDY29E!#92ꢀ
G1:A"H3D9=1D"Aꢀ"A=%!,9=,1A9Gꢀ"#2ꢀ9#23WGꢀ,%9ꢀA9G1D,!#&ꢀ:3D;H9AGꢀW!,%ꢀ%!&%9AꢀG,"X!D!,;ꢀ
!
#ꢀ =3H:"A!G3#ꢀ W!,%ꢀ 3,%9Aꢀ #3#=3L"D9#,ꢀ !#,9A"=,!3#GBNeYSN
33A2!#",!3#Y2A!L9#ꢀ:3D;H9AGꢀ=31D2ꢀ=3HX!#9ꢀ,%9ꢀ:A3:9A,!9Gꢀ3Eꢀ3A&"#!=ꢀ:3D;H9AGꢀW!,%ꢀ
%9ꢀ:%3,3:%;G!="D'ꢀH"&#9,!='ꢀ9D9=,A3#!='ꢀ"#2ꢀ=","D;,!=ꢀ:3,9#,!"Dꢀ3EꢀH9,"DGBꢀ-%9ꢀ
ꢀ
F9"#W%!D9'ꢀ
=
,
=%9H!G,A;ꢀ3EꢀH9,"DY,9A:;A!2!#9ꢀ=3H:D9]9Gꢀ!Gꢀ"ꢀ:"A,!=1D"AD;ꢀ:3W9AE1Dꢀ,33DꢀE3Aꢀ,%9ꢀ
X1!D2!#&ꢀ3EꢀG1:A"H3D9=1D"Aꢀ"A=%!,9=,1A9Gꢀ"#2ꢀ:3D;H9AG'ꢀG!#=9ꢀ,9A:;A!2!#9ꢀH3!9,!9Gꢀ"A9ꢀ
=
":"XD9ꢀ3EꢀE3AH!#&ꢀG,A3#&'ꢀ2!A9=,92ꢀ"#2ꢀA9L9AG!XD9ꢀ=3H:D9]9GꢀW!,%ꢀ"ꢀL"A!9,;ꢀ3EꢀH9,"Dꢀ
?
!
3#Gꢀ219ꢀ,3ꢀ2fY:f ꢀX"=TYX3#2!#&ꢀ3Eꢀ,%9ꢀH9,"Dꢀ,3ꢀ:;A!2!#9ꢀA!#&Gꢀ"#2ꢀ,%9ꢀ=%9D",9ꢀ
9
EE9=,BSSYSUꢀV3Aꢀ9]"H:D9'ꢀ<=%1X9A,ꢀ"#2ꢀ=3W3AT9AGꢀA9:3A,92ꢀ"ꢀD!#9"AꢀW",9AYG3D1XD9ꢀ
H9,"DD3YG1:A"H3D9=1D"Aꢀ:3D;H9AꢀX"G92ꢀ3#ꢀ!A3#Z[[\h,9A:;A!2!#9ꢀ=3H:D9]9G'ꢀW%!=%ꢀ
G%3W92ꢀ%!&%ꢀ,%9AH"DꢀG,"X!D!,;ꢀ"#2ꢀA9L9AG!XD9ꢀ:A3:9A,!9GBSS
<1:A"H3D9=1D"Aꢀ:3D;&3#Gꢀ"#2ꢀ:3D;%92A3#GꢀW!,%ꢀW9DDY29E!#92ꢀG!J9G'ꢀG%":9Gꢀ"#2ꢀ
!
ACS Paragon Plus Environment

Page 3 of 19
Journal of the American Chemical Society
1
2
3
4
5
6
7
8
9
&
93H9,A!9Gꢀ=31D2ꢀX9ꢀA9"2!D;ꢀ=3#G,A1=,92ꢀL!"ꢀ,%9ꢀH9,"DYD!&"#2ꢀ=33A2!#",!3#Y2A!L9#ꢀ
G9DEY"GG9HXD;BSeYRSꢀKG!#&ꢀ"ꢀG9D9=,!L9ꢀ"#2ꢀA9"G3#"XD9ꢀ=%3!=9ꢀ3Eꢀ:A9=1AG3AG'ꢀ<,"#&'Seꢀ
MO
MM
SU
V1/!,"' ꢀ0";H3#2' ꢀ4!,G=%T9' ꢀ"#2ꢀ3,%9AGꢀ%"L9ꢀ29G!&#92ꢀ"#2ꢀG;#,%9G!J92ꢀ"ꢀD!XA"A;ꢀ
3
Eꢀ9D9&"#,ꢀ,W3Y2!H9#G!3#"DꢀH9,"DD"=;=D9Gꢀ"#2ꢀ,%A99Y2!H9#G!3#"DꢀH9,"DD"="&9G'ꢀW%!=%ꢀ
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
"
=
A9ꢀ!#=A9"G!#&D;ꢀ3Eꢀ!#,9A9G,ꢀ!#ꢀL"A!31Gꢀ"::D!=",!3#GꢀG1=%ꢀ"Gꢀ9#=":G1D",!3#'ꢀ=","D;G!G'ꢀ
%9H3G9#G!#&'ꢀ"#2ꢀD!&%,ꢀ%"AL9G,!#&Bꢀa9="1G9ꢀ3Eꢀ,%9ꢀW9DDY29E!#92ꢀG,A1=,1A9Gꢀ3Eꢀ
H9,"DD"=;=D9G'ꢀH1D,!:D9ꢀE1#=,!3#"DꢀH3!9,!9Gꢀ="#ꢀX9ꢀ9"G!D;ꢀ=3L"D9#,D;ꢀ"::9#292ꢀ9!,%9Aꢀ
#ꢀ,%9ꢀ:9A!:%9A;ꢀ3Aꢀ",ꢀ,%9ꢀL9A,!=9Gꢀ3Eꢀ:A929G!&#92ꢀH9,"DD"=;=D!=ꢀGT9D9,3#G'ꢀW%!=%ꢀ
"EE3A2ꢀ,%9ꢀ=%"#=9ꢀ,3ꢀ!#,A321=9ꢀ3,%9Aꢀ,;:9Gꢀ3Eꢀ#3#=3L"D9#,ꢀ!#,9A"=,!3#GꢀE3Aꢀ3A,%3&3#"Dꢀ
!9A"A=%!="Dꢀ G9DEY"GG9HXD;BRMYRPꢀ i!"ꢀ 3A,%3&3#"Dꢀ =3HX!#",!3#ꢀ 3Eꢀ H9,"DYD!&"#2ꢀ
33A2!#",!3#Y2A!L9#ꢀG9DEY"GG9HXD;ꢀW!,%ꢀ3,%9Aꢀ2!EE9A9#,ꢀ#3#=3L"D9#,ꢀ!#,9A"=,!3#G'ꢀ
3
%
=
H1D,!E1#=,!3#"DꢀH9,"DD"=;=D9Yꢀ3AꢀH9,"DD"="&9Y=3A92ꢀG1:A"H3D9=1D"Aꢀ:3D;H9AGꢀ=31D2ꢀX9ꢀ
A9"2!D;ꢀ"==9GG92BNP'RQ'R`ꢀV3Aꢀ9]"H:D9'ꢀ<,"#&ꢀ"#2ꢀ=3W3AT9AGꢀA9:3A,92ꢀG9L9A"DꢀE1#=,!3#"Dꢀ
G1:A"H3D9=1D"Aꢀ :3D;H9AGꢀ W!,%ꢀ E"G=!#",!#&ꢀ :A3:9A,!9Gꢀ X;ꢀ ,%9ꢀ 1#!E!=",!3#ꢀ 3Eꢀ
:D",!#1HZ[[\YD!&"#2ꢀ=33A2!#",!3#Y2A!L9#ꢀG9DEY"GG9HXD;ꢀW!,%ꢀ%;2A3&9#ꢀX3#2!#&ꢀ3Aꢀ
=
A3W#ꢀ9,%9AYX"G92ꢀ%3G,b&19G,ꢀ!#,9A"=,!3#GBRM'RUYQOꢀ83W9L9A'ꢀ!,ꢀ!GꢀG,!DDꢀL9A;ꢀ=%"DD9#&!#&ꢀ
3ꢀ:A9:"A9ꢀ,%9ꢀW9DDY=3#,A3DD92ꢀ%!9A"A=%!="DꢀG9DEY"GG9HXD;ꢀ3Eꢀ3A&"#3H9,"DD!=ꢀH",9A!"DGꢀ
W!,%ꢀ%!&%9AY3A29AꢀG,A1=,1A9G'ꢀ9G:9=!"DD;ꢀ,%9ꢀG,!H1D!YA9G:3#G!L9ꢀGH"A,ꢀG3E,ꢀH",9A!"DGBꢀ
,
<
1:9AG,A1=,1A9Gꢀ"GG9HXD92ꢀL!"ꢀ,%A99ꢀ3AꢀH3A9ꢀ,;:9Gꢀ3Eꢀ3A,%3&3#"Dꢀ#3#=3L"D9#,ꢀ
QN
!
#,9A"=,!3#Gꢀ,%",ꢀ23ꢀ#3,ꢀ!#,9AE9A9ꢀW!,%ꢀ3#9ꢀ"#3,%9A'ꢀ"A9ꢀA"A9D;ꢀA9:3A,92B ꢀK:ꢀ,3ꢀ#3W'ꢀ
1G1"DD;ꢀ3#D;ꢀ3#9ꢀ,;:9ꢀ3EꢀH9,"DYD!&"#2ꢀX!#2!#&ꢀH3,!EꢀW"Gꢀ!#=3A:3A",92ꢀ!#ꢀ,%3G9ꢀ
G,A1=,1A9GBꢀ[,ꢀ!Gꢀ!#,A!&1!#&ꢀ,3ꢀE1#=,!3#"D!J9ꢀ,%9ꢀ"A=%!,9=,1A9GꢀW!,%ꢀG9=3#2"A;ꢀH9,"DꢀG!,9G'ꢀ
W%!=%ꢀ =31D2ꢀ E1A#!G%ꢀ ,%9ꢀ H",9A!"DGꢀ W!,%ꢀ H3A9ꢀ #3L9Dꢀ E1#=,!3#"D!,!9G'ꢀ G1=%ꢀ "Gꢀ
9
D9=,A3=%9H!="D'ꢀ:%3,3:%;G!="Dꢀ3AꢀH"&#9,!=ꢀ:A3:9A,!9GBQS
9A9!#'ꢀ!#ꢀ"22!,!3#ꢀ,3ꢀ:D",!#1HZ[[\ :;A!2!#9ꢀ=33A2!#",!3#ꢀH3,!E'ꢀW9ꢀ!#,A321=92ꢀ"ꢀ
8
G9=3#2ꢀ=33A2!#",!3#ꢀH3,!E'ꢀ,%9ꢀ,9A:;A!2!#9YJ!#=Z[[\ꢀ=3H:D9]ꢀ,3ꢀ,%9ꢀX"=TX3#9ꢀ3Eꢀ,%9ꢀ
G1:A"H3D9=1D"Aꢀ:3D;H9AGBꢀ-3ꢀ,%!Gꢀ9#2'ꢀ"ꢀ%9,9A3H9,"DD!=ꢀ=A3GGYD!#T92ꢀG1:A"H3D9=1D"Aꢀ
:
3D;H9AꢀW"Gꢀ=3#G,A1=,92ꢀX;ꢀ,%9ꢀ%!9A"A=%!="Dꢀ1#!E!=",!3#ꢀ3Eꢀ,%A99ꢀ,;:9Gꢀ3Eꢀ#3#=3L"D9#,ꢀ
!
#,9A"=,!3#G'ꢀ :D",!#1HZ[[\YD!&"#2ꢀ =33A2!#",!3#Y2A!L9#ꢀ G9DEY"GG9HXD;'ꢀ
J!#=Z[[\Y,9A:;A!2!#9ꢀ=3H:D9]ꢀ"#2ꢀ%3G,^&19G,ꢀ!#,9A"=,!3#GBꢀꢁGꢀG%3W#ꢀ!#ꢀ<=%9H9ꢀN'ꢀ
"
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 4 of 19
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
2
!,3:!=ꢀD!&"#2GꢀW!,%ꢀ3#9ꢀ9#2ꢀ,9AH!#",!#&ꢀW!,%ꢀ"ꢀ,9A:;A!2;DꢀH3!9,;ꢀ"#2ꢀ,%9ꢀ3,%9Aꢀ
,
9AH!#",!#&ꢀW!,%ꢀ"ꢀNSOjꢀ2!:;A!2;DꢀEA"&H9#,'ꢀX9"A!#&ꢀ2!EE9A9#,ꢀG1XG,!,19#,GꢀW9A9ꢀ
G;#,%9G!J92'ꢀW%9A9!#ꢀ:D",!#1HZ[[\ꢀ=31D2ꢀX!#2ꢀ,3ꢀ,%9ꢀNSOjꢀ2!:;A!2;DꢀH3!9,;ꢀ,3ꢀE3AHꢀ
A%3HX3!2"DꢀH9,"DD"=;=D9G'ꢀ"#2ꢀ,%9#ꢀ,%9ꢀ,9AH!#"Dꢀ,9A:;A!2!#9Gꢀ="#ꢀ=33A2!#",9ꢀW!,%ꢀ
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
$
#Z[[\ꢀ!#,3ꢀD!#9"AꢀG1:A"H3D9=1D"Aꢀ:3D;H9AGBꢀ-3ꢀ,%9ꢀX9G,ꢀ3Eꢀ31AꢀT#3WD92&9'ꢀ,%!Gꢀ!Gꢀ,%9ꢀ
E!AG,ꢀ,!H9ꢀ,3ꢀ29L9D3:ꢀD!#9"AꢀG1:A"H3D9=1D"Aꢀ:3D;H9AGꢀW!,%ꢀ%9,9A3H9,"DD!=ꢀX!=;=D!=ꢀ
H9,"DD"=;=D9Gꢀ!#ꢀ,%9ꢀX"=TX3#9Bꢀ-%9ꢀ=3#/1&",!3#ꢀD9#&,%ꢀW"Gꢀ9],9#292ꢀ"E,9Aꢀ,%9ꢀ
J!#=Y,9A:;A!2!#9ꢀ=3H:D9]9GꢀE3AH92'ꢀW%!=%ꢀA92G%!E,92ꢀ,%9ꢀ"XG3A:,!3#ꢀ"#2ꢀ9H!GG!3#ꢀ
G:9=,A"Bꢀ-%9#'ꢀ"ꢀG1:A"H3D9=1D"Aꢀ:3D;H9Aꢀ#9,W3ATꢀ&9DꢀW"Gꢀ3X,"!#92ꢀX;ꢀ"22!#&ꢀ,%9ꢀ
=
A3GGYD!#T9A'ꢀX!GY"HH3#!1HꢀG"D,'ꢀ,3ꢀ,%9ꢀG3D1,!3#ꢀ3Eꢀ,%9ꢀD!#9"AꢀG1:A"H3D9=1D"Aꢀ:3D;H9ABꢀ
%9ꢀ=A3GGYD!#T92ꢀG1:A"H3D9=1D"Aꢀ:3D;H9AꢀW"GꢀE31#2ꢀ,3ꢀE3AHꢀG1:A"H3D9=1D"Aꢀ&9DGꢀ",ꢀ
!&%ꢀ=3#=9#,A",!3#Gꢀ!#ꢀ"::A3:A!",9ꢀG3DL9#,G'ꢀ29H3#G,A",!#&ꢀ,%",ꢀH1D,!YE1#=,!3#"DꢀGH"A,ꢀ
G3E,ꢀH",9A!"DGꢀ=31D2ꢀX9ꢀ"==9GG92ꢀ1G!#&ꢀ,%9ꢀG,A",9&;ꢀ29L9D3:92ꢀ%9A9BꢀV1A,%9AH3A9'ꢀ,%9ꢀ
%3,3:%;G!="Dꢀ :A3:9A,!9Gꢀ 3Eꢀ ,%9ꢀ H9,"DD"=;=D9Gꢀ "#2ꢀ =A3GGYD!#T92ꢀ G1:A"H3D9=1D"Aꢀ
-
%
:
:3D;H9AGꢀ=31D2ꢀX9ꢀ9EE9=,!L9D;ꢀ,1#92ꢀL!"ꢀ=%"#&!#&ꢀ,%9ꢀG1XG,!,19#,Gꢀ3#ꢀ,%9ꢀ:A9=1AG3Aꢀ
D!&"#2GB
#
ACS Paragon Plus Environment

Page 5 of 19
Journal of the American Chemical Society
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
.
7!-!ꢀꢁꢀC"A,33#ꢀA9:A9G9#,",!3#ꢀ3Eꢀ,%9ꢀE3AH",!3#ꢀ3EꢀA%3HX3!2"DꢀH9,"DD"=;=D9G'ꢀ"ꢀ
D!#9"AꢀG1:A"H3D9=1D"Aꢀ:3D;H9Aꢀ"#2ꢀ"ꢀ=A3GGYD!#T92ꢀM+ꢀG1:A"H3D9=1D"Aꢀ:3D;H9A!=ꢀ
Sd
#
9,W3ATꢀEA3HꢀH9,"DD"=;=D9G'ꢀ$# ꢀ"#2ꢀX!GY"HH3#!1HꢀG"D,GB
=B @C8 ꢀA>?ꢀ?: 4@ :9>
-%9ꢀA%3HX3!2"DꢀH9,"DD"=;=D9GꢀW9A9ꢀ3X,"!#92ꢀX;ꢀG,!AA!#&ꢀ"ꢀH!],1A9ꢀ3Eꢀ,%9ꢀNSOjꢀ
2
!:;A!2;Dꢀ %9,9A32!,3:!=ꢀ D!&"#2ꢀ ꢁ&$ꢁ5ꢀ "#2ꢀ "#ꢀ 9k1!H3D"Aꢀ "H31#,ꢀ 3Eꢀ POjꢀ
3
3
A&"#3Y2!:D",!#1HꢀZ[[\ꢀ"==9:,3AꢀDꢀ!#ꢀ+F<lY ꢀ",ꢀPQꢀ CꢀE3AꢀNSꢀ%Bꢀ-%9G9ꢀA%3HX3!2Gꢀ
P
W9A9ꢀ:9#29#,ꢀW!,%ꢀX9#J3YSNY=A3W#Y`ꢀZaSNC`\ꢀ",ꢀ,%9!Aꢀ"=1,9ꢀL9A,!=9Gꢀ"#2ꢀ,9A:;A!2!#9ꢀ
H3!9,!9Gꢀ",ꢀ,%9!Aꢀ3X,1G9ꢀL9A,!=9G'ꢀA9G:9=,!L9D;Bꢀ-%9ꢀ29,"!D92ꢀG;#,%9,!=ꢀ:A3=921A9GꢀE3Aꢀ
,
%9ꢀD!&"#2Gꢀ"#2ꢀH9,"DD"=;=D9Gꢀ"A9ꢀ&!L9#ꢀ!#ꢀ,%9ꢀ<1::3A,!#&ꢀ[#E3AH",!3#ꢀZ<[\Bꢀ-%9G9ꢀ
=%9H!="DꢀG,A1=,1A9Gꢀ3Eꢀ,%9ꢀD!&"#2Gꢀ"#2ꢀ,%9ꢀE3AH",!3#ꢀ3Eꢀ2!G=A9,9ꢀ"#2ꢀ%!&%D;ꢀG;HH9,A!=ꢀ
N
MN
G:9=!9GꢀW9A9ꢀ=3#E!AH92ꢀX;ꢀH1D,!#1=D9"AꢀZ8ꢀ"#2ꢀ @\ꢀ4F0ꢀ"#"D;G9GꢀZV!&1A9ꢀ<NY<MU\Bꢀ
N
8
9A9'ꢀW9ꢀ1G9ꢀE&ꢀ"Gꢀ"ꢀA9:A9G9#,",!L9ꢀ9]"H:D9Bꢀ[#ꢀ,%9ꢀ 8ꢀ4F0ꢀG:9=,A1Hꢀ3Eꢀ
H9,"DD"=;=D9ꢀE&ꢀZV!&1A9ꢀN"YN=\'ꢀ,%9ꢀ:A3,3#Gꢀ3Eꢀ,%9ꢀ:;A!2;Dꢀ&A31:Gꢀ9]%!X!,92ꢀ23W#E!9D2ꢀ
$
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 6 of 19
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
G%!E,Gꢀ=3H:"A92ꢀW!,%ꢀ,%3G9ꢀ3Eꢀ,%9ꢀEA99ꢀD!&"#2ꢀꢁ&ꢀ219ꢀ,3ꢀ,%9ꢀD3GGꢀ3Eꢀ9D9=,A3#ꢀ29#G!,;ꢀ
1
:3#ꢀ=33A2!#",!3#ꢀ3Eꢀ,%9ꢀ:;A!2!#9ꢀ4ꢀ",3HꢀW!,%ꢀ,%9ꢀ:D",!#1HꢀZ[[\ꢀ=9#,9AGBꢀa9G!29G'ꢀ"ꢀ
G:D!,,!#&ꢀ3Eꢀ,%9ꢀ8ꢀ"#2ꢀ8ꢀ:9"TGꢀW"Gꢀ3XG9AL92ꢀZ8ꢀEA3HꢀUBPUꢀ,3ꢀeBOOꢀ"#2ꢀUBeOꢀ::Hmꢀ8ꢀ
!
"
!
"
EA3Hꢀ`BQQꢀ,3ꢀUBRQꢀ"#2ꢀUBMMꢀ::H\Bꢀ-%9ꢀ"GG!&#H9#,ꢀ"#2ꢀ=3AA9D",!3#ꢀ3Eꢀ,%9ꢀ:A3,3#Gꢀ3#ꢀ
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
N
N
,
%9ꢀH9,"DD"=;=D9ꢀW"GꢀL"D!2",92ꢀX;ꢀ 8Y8ꢀ%3H3#1=D9"Aꢀ=3AA9D",!3#ꢀG:9=,A3G=3:;ꢀ
MN
ZCl<>\ꢀ4F0ꢀ9]:9A!H9#,GꢀZV!&1A9ꢀ<Se\Bꢀ-%9ꢀ @ꢀ4F0ꢀG:9=,A1Hꢀ3EꢀA%3HX3!2ꢀE&ꢀ
G%3W92ꢀ"ꢀG%"A:ꢀG!#&D9,ꢀ",ꢀNRBNOꢀ::HꢀW!,%ꢀ=3#=3H!,"#,ꢀNeQ@,ꢀG",9DD!,9GꢀZ#@,Y@ꢀnꢀSP`UBNꢀ
8J\'ꢀ!#ꢀ"==3A2"#=9ꢀW!,%ꢀ"ꢀG!#&D9ꢀ:%3G:%3A31Gꢀ9#L!A3#H9#,Bꢀ-%!Gꢀ:9"TꢀW"Gꢀ1:E!9D2ꢀ
G%!E,92ꢀX;ꢀPBOSꢀ::HꢀA9D",!L9ꢀ,3ꢀ,%",ꢀ3Eꢀ,%9ꢀ:D",!#1HZ[[\ꢀ"==9:,3AꢀZV!&1A9ꢀN2ꢀ"#2ꢀN9\Bꢀ
ID9=,A3G:A";ꢀ!3#!J",!3#ꢀ,!H9Y3EYED!&%,ꢀH"GGꢀG:9=,A3H9,A;ꢀZI<[Y-lVYF<\ꢀE1A,%9Aꢀ
2
9H3#G,A",92ꢀ,%9ꢀG,3!=%!3H9,A;ꢀ3Eꢀ,%9ꢀE3AH",!3#ꢀ3EꢀA%3HX3!2GꢀZV!&1A9ꢀNE\Bꢀꢁ#ꢀ
!
G3,3:!="DD;ꢀA9G3DL92ꢀ:9"Tꢀ=3AA9G:3#2!#&ꢀ,3ꢀ,%9ꢀ!#,"=,ꢀ"#2ꢀ2!G=A9,9ꢀoSꢀdꢀSpꢀ"GG9HXD;ꢀ
Y
E&ꢀW!,%ꢀ,%9ꢀD3GGꢀ3Eꢀ,%A99ꢀ,A!ED13A3H9,%"#9G1DE3#",9ꢀZl-E\ꢀ=31#,9A!3#GꢀW"Gꢀ3XG9AL92ꢀ
Md
"
,ꢀ$h%ꢀNSR`BSOꢀoFꢀbꢀMl-Ep 'ꢀW%!=%ꢀ:A3L!292ꢀ=3#L!#=!#&ꢀ9L!29#=9ꢀE3Aꢀ,%9ꢀ9]!G,9#=9ꢀ
3Eꢀ,%9ꢀA%3HX3!2"DꢀH9,"DD"=;=D9ꢀ"Gꢀ,%9ꢀ3#D;ꢀG1:A"H3D9=1D"AꢀG:9=!9GBꢀ6!T9W!G9'ꢀ"DDꢀ3,%9Aꢀ
H9,"DD"=;=D9Gꢀ&"L9ꢀ,%9ꢀG!H!D"AꢀA9G1D,Gꢀ"GꢀG%3W#ꢀ!#ꢀ,%9ꢀ<[B
%
ACS Paragon Plus Environment

Page 7 of 19
Journal of the American Chemical Society
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
N
MN
F')/+!ꢀꢁGꢀ@"A,!"DꢀZ"Y=\ꢀ8ꢀ"#2ꢀZ2'ꢀ9\ꢀ @ꢀ4F0ꢀG:9=,A"ꢀoC+
M
C4hC+
S
CD
S
ꢀZNqN'ꢀ&h&\'ꢀSeQꢀcpꢀ3EꢀZ"\ꢀꢁ&'ꢀ
ZX'ꢀ9\ꢀE&'ꢀZ='ꢀ2\ꢀ"==9:,3AꢀDBꢀZE\ꢀI]:9A!H9#,"DꢀZA92\ꢀ"#2ꢀ="D=1D",92ꢀZXD19\ꢀI<[Y-lVYF<ꢀG:9=,A"ꢀ3Eꢀ
A%3HX3!2"DꢀH9,"DD"=;=D9ꢀE&ꢀoFꢀbꢀMl-EpMdB
<1XG9k19#,D;'ꢀ ,%9ꢀ D!#9"Aꢀ G1:A"H3D9=1D"Aꢀ :3D;H9Aꢀ H&ꢀ W"Gꢀ E3AH92ꢀ X;ꢀ ,%9ꢀ
=33A2!#",!3#ꢀX9,W99#ꢀ$#Zl-E\ꢀ"#2ꢀ,9A:;A!2!#9ꢀH3!9,!9G'ꢀW%!=%ꢀW"Gꢀ!#L9G,!&",92ꢀX;ꢀ
S
KiYi!GꢀG:9=,A3G=3:;BꢀꢁꢀKiYi!Gꢀ,!,A",!3#ꢀW"Gꢀ:9AE3AH92ꢀX;ꢀG,9:W!G9ꢀ"22!#&ꢀ"ꢀ
G3D1,!3#ꢀ3Eꢀ$#Zl-E\ꢀ,3ꢀ"ꢀC8CDhC8C4ꢀG3D1,!3#ꢀ3EꢀE&ꢀZV!&1A9ꢀS"\Bꢀ-%9ꢀ"XG3AX"#=9ꢀ
S
S
S
M
3
&
Eꢀ,%9ꢀX"#2ꢀ",ꢀMeSꢀ#Hꢀ=3AA9G:3#2!#&ꢀ,3ꢀ,%9ꢀ=%"A"=,9A!G,!=ꢀ3EꢀJ!#=Y,9A:;A!2!#9ꢀ=3H:D9]ꢀ
A"21"DD;ꢀ!#=A9"G92'ꢀ"#2ꢀ"ꢀ2!G,!#=,ꢀ!G3GX9G,!=ꢀ:3!#,ꢀ",ꢀMROꢀ#Hꢀ"::9"A92'ꢀ!#2!=",!#&ꢀ,%9ꢀ
G1==9GGE1DꢀE3AH",!3#ꢀ3Eꢀ,%9ꢀJ!#=Y,9A:;A!2!#9ꢀ=3H:D9]9GBꢀꢁGꢀG%3W#ꢀ!#ꢀV!&1A9ꢀSX'ꢀ,%9ꢀ
"XG3AX"#=9ꢀ",ꢀMeSꢀ#Hꢀ"DH3G,ꢀA9H"!#92ꢀ=3#G,"#,ꢀ"E,9Aꢀ,%9ꢀ"22!,!3#ꢀ3Eꢀ3#9ꢀ9k1!L"D9#,ꢀ3Eꢀ
&
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 8 of 19
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
ACS Paragon Plus Environment

Page 9 of 19
Journal of the American Chemical Society
1
2
3
4
5
6
7
8
9
=
"
3H:D9]",!3#ꢀX9,W99#ꢀ=A3W#ꢀ9,%9Aꢀ"#2ꢀ,%9ꢀG9=3#2"A;ꢀ"HH3#!1HꢀG"D,ꢀW"GꢀG9D9=,92ꢀ"Gꢀ
ꢀH329DꢀG;G,9Hꢀ,3ꢀG,12;ꢀ,%9ꢀX!#2!#&ꢀG,A9#&,%ꢀ21A!#&ꢀG1:A"H3D9=1D"Aꢀ:3D;H9A!J",!3#ꢀ
ZV!&1A9ꢀ<RM\Bꢀ-%9ꢀ:A3,3#Gꢀ8 ꢀ"#2ꢀ8 ꢀ3#ꢀ,%9ꢀX!GY"HH3#!1HꢀKꢀ23W#E!9D2ꢀG%!E,92'ꢀ
R_
P_
W%!D9ꢀ,%9ꢀG!&#"DGꢀ3Eꢀ,%9ꢀ:A3,3#Gꢀ3#ꢀ,%9ꢀ=A3W#ꢀ9,%9Aꢀ3EꢀDꢀ1:E!9D2ꢀG%!E,92Bꢀ-%9ꢀ
GG3=!",!3#ꢀ =3#G,"#,ꢀ X9,W99#ꢀ Dꢀ "#2ꢀ ,%9ꢀ H3#3Y"HH3#!1Hꢀ Lꢀ ZV!&1A9ꢀ <RR\ꢀ !#ꢀ
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
"
N
S
YN
C+C4hC+CDꢀ29,9AH!#92ꢀX;ꢀ"ꢀ 8ꢀ4F0ꢀH9,%32ꢀW"GꢀRBPꢀZsꢀNBQ\ꢀrꢀNOꢀF 'ꢀW%!=%ꢀ
M
S
S
!
#2!=",92ꢀ ,%",ꢀ ,%9ꢀ %3G,Y&19G,ꢀ !#,9A"=,!3#ꢀ G1!,"XD9ꢀ E3Aꢀ ,%9ꢀ =3#G,A1=,!3#ꢀ 3Eꢀ ,%9ꢀ
=
A3GGYD!#T92ꢀG1:A"H3D9=1D"Aꢀ"GG9HXD!9GꢀZV!&1A9ꢀ<RQꢀ"#2ꢀ<RP\Bꢀ
-%9ꢀ=3#L9AG!3#ꢀEA3HꢀD!#9"Aꢀ,3ꢀ=A3GGYD!#T92ꢀG1:A"H3D9=1D"Aꢀ:3D;H9AGꢀW"Gꢀ,%9#ꢀ
N
"
==3H:D!G%92ꢀX;ꢀ"22!#&ꢀ"ꢀX!GY"HH3#!1HꢀD!#T9AꢀKBꢀC3#=9#,A",!3#Y29:9#29#,ꢀ8ꢀ4F0ꢀ
H9"G1A9H9#,GꢀW9A9ꢀ:9AE3AH92ꢀ,3ꢀ!#L9G,!&",9ꢀ,%9ꢀE3AH",!3#ꢀ3Eꢀ,%9ꢀ=A3GGYD!#T92ꢀ
G1:A"H3D9=1D"Aꢀ:3D;H9Aꢀ"GꢀG%3W#ꢀ!#ꢀV!&1A9ꢀMBꢀꢁꢀNqNꢀH!],1A9ꢀ3EꢀH&ꢀ"#2ꢀKꢀW"Gꢀ=%3G9#ꢀ
"
=
Gꢀ,%9ꢀ3#G9,Bꢀg!,%ꢀ,%9ꢀ!#=A9"G!#&ꢀH3#3H9Aꢀ=3#=9#,A",!3#'ꢀ#3,!=9"XD9ꢀ=%9H!="DꢀG%!E,ꢀ
%"#&9GꢀE3AꢀX3,%ꢀ:A9=1AG3AGꢀW9A9ꢀ3XG9AL92BꢀK:E!9D2ꢀG%!E,GꢀW9A9ꢀ3XG9AL92ꢀE3Aꢀ,%9ꢀ
G!&#"DGꢀ3Eꢀ8ꢀ"#2ꢀ8ꢀ3EꢀH&'ꢀW%9A9"Gꢀ,%9ꢀ8 ꢀ"#2ꢀ8 ꢀ3Eꢀ,%9ꢀX!GY"HH3#!1HꢀD!#T9AꢀKꢀ
R
Q
R_
P_
G%!E,92ꢀ23W#E!9D2Bꢀ-%9ꢀ:9"TGꢀ3Eꢀ"DDꢀ,%9ꢀ:A3,3#ꢀG!&#"DGꢀX9="H9ꢀXA3"29Aꢀ"Gꢀ,%9ꢀH3#3H9Aꢀ
3#=9#,A",!3#Gꢀ!#=A9"G92'ꢀG1&&9G,!#&ꢀ,%9ꢀ&A"21"DꢀE3AH",!3#ꢀ3Eꢀ,%9ꢀ=A3GGYD!#T92ꢀ
G1:A"H3D9=1D"Aꢀ:3D;H9ABꢀV1A,%9AH3A9'ꢀ,%9G9ꢀ3XG9AL",!3#Gꢀ"DG3ꢀ!#2!=",9ꢀ,%",ꢀ,%9ꢀ@,t4ꢀ
33A2!#",!3#'ꢀ,%9ꢀ,9A:;A!2!#9YH9,"Dꢀ=33A2!#",!3#ꢀ"#2ꢀ,%9ꢀ%3G,^&19G,ꢀ!#,9A"=,!3#ꢀ23#_,ꢀ
#,9AE9A9ꢀW!,%ꢀ9"=%ꢀ3,%9Aꢀ!#ꢀ,%!GꢀG;G,9HB
=
=
!
(
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 10 of 19
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
N
M S S
F')/+!ꢀEGꢀ@"A,!"Dꢀ8ꢀ4F0ꢀG:9=,A"ꢀZC+C4hC+CD'ꢀNhN'ꢀ&)&'ꢀSeQꢀc'ꢀQOOꢀF8J\ꢀ3EꢀZ"\ꢀH&'ꢀZ/\ꢀKꢀ"#2ꢀꢀ
ZXY!\ꢀM&ꢀZ3AꢀNqNꢀH!],1A9ꢀ3EꢀH&ꢀ"#2ꢀK\ꢀ",ꢀ,%9ꢀ=3#=9#,A",!3#ꢀ3EꢀaSNC`ꢀ1#!,ꢀ3EꢀZX\ꢀNꢀHFꢀZ=\ꢀQꢀHFꢀZ2\ꢀ
NOꢀHFꢀZ9\ꢀSOꢀHFꢀZE\ꢀMOꢀHFꢀZ&\ꢀROꢀHFꢀZ%\ꢀQOꢀHFꢀZ!\ꢀPOꢀHFB
<
!H!D"AD;'ꢀ+l<>ꢀ"#2ꢀ+6<ꢀH9"G1A9H9#,GꢀW9A9ꢀ="AA!92ꢀ31,ꢀ,3ꢀ29H3#G,A",9ꢀ,%9ꢀ
E3AH",!3#ꢀ3Eꢀ,%9ꢀ=A3GGYD!#T92ꢀG1:A"H3D9=1D"Aꢀ:3D;H9AꢀM&ꢀ!#ꢀG3D1,!3#BꢀVA3HꢀV!&1A9ꢀR"'ꢀ
Gꢀ,%9ꢀ=3#=9#,A",!3#ꢀ3EꢀaSNC`h"HH3#!1HꢀG"D,ꢀ1#!,Gꢀ!#ꢀ,%9ꢀG1:A"H3D9=1D"Aꢀ:3D;H9Aꢀ
"
YNO
YNN
S
YN
!
#=A9"G92ꢀEA3HꢀQꢀ,3ꢀPOꢀHF'ꢀ(ꢀ29=A9"G92ꢀEA3HꢀSBUꢀrꢀNO ꢀ,3ꢀPBSꢀrꢀNO ꢀHꢀG BꢀVA3Hꢀ
V!&1A9ꢀRX'ꢀ"Gꢀ,%9ꢀ=3#=9#,A",!3#ꢀ3EꢀaSNC`h"HH3#!1HꢀG"D,ꢀ1#!,Gꢀ!#=A9"G92ꢀEA3HꢀSꢀ,3ꢀPOꢀ
HF'ꢀ( ꢀ!#=A9"G92ꢀEA3HꢀNOeꢀ,3ꢀ`NQꢀ#H'ꢀW%!=%ꢀW9A9ꢀG!&#!E!="#,D;ꢀD"A&9Aꢀ,%"#ꢀ,%3G9ꢀ3Eꢀ
%
H&ꢀ1#29Aꢀ,%9ꢀG"H9ꢀ=3#=9#,A",!3#Gꢀ 3EꢀaSNC`ꢀ1#!,GꢀZV!&1A9ꢀ<R`\Bꢀ-%9G9ꢀA9G1D,Gꢀ
2
9H3#G,A",9ꢀ,%9ꢀE3AH",!3#ꢀ3Eꢀ"ꢀ=A3GGYD!#T92ꢀG1:A"H3D9=1D"Aꢀ:3D;H9ABꢀ0%93D3&!="Dꢀ
]:9A!H9#,Gꢀ3#ꢀ,%9ꢀA9G1D,!#&ꢀ&9DGꢀW9A9ꢀ"DG3ꢀ=3#21=,92ꢀ,3ꢀG,12;ꢀ,%9ꢀL!G=39D"G,!=ꢀ
A3:9A,!9GꢀZV!&1A9ꢀR=\Bꢀ-%9ꢀG,3A"&9ꢀH321D1GꢀZ*u\ꢀ!Gꢀ"DW";GꢀD"A&9Aꢀ,%"#ꢀ,%9ꢀD3GGꢀ
9
:
H321D1GꢀZ*v\ꢀ"#2ꢀX3,%ꢀ"A9ꢀ!#29:9#29#,ꢀ3Eꢀ,%9ꢀ"#&1D"AꢀEA9k19#=;ꢀ+'ꢀ!#2!=",!L9ꢀ3Eꢀ,%9ꢀ
E3AH",!3#ꢀ3Eꢀ3A&"#3&9DGBꢀꢁ22!,!3#"DD;'ꢀ,%9ꢀ<IFꢀ!H"&9ꢀ"GꢀG%3W#ꢀ!#ꢀV!&1A9ꢀR2ꢀ
A9L9"D92ꢀ"#ꢀ9],9#292ꢀ"#2ꢀ!#,9A=3##9=,92ꢀE!XA31Gꢀ#9,W3ATꢀE3Aꢀ,%9ꢀ]9A3&9Dꢀ:A9:"A92ꢀX;ꢀ
"
ꢀEA99J9Y2A;!#&ꢀH9,%32'ꢀ&!L!#&ꢀ2!A9=,ꢀ9L!29#=9ꢀE3Aꢀ,%9ꢀE3AH",!3#ꢀ3Eꢀ,%9ꢀ=A3GGYD!#T92ꢀ
)
ACS Paragon Plus Environment

Page 11 of 19
Journal of the American Chemical Society
1
2
3
4
5
6
7
8
9
#
9,W3ATGꢀ3EꢀM&Bꢀ
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
F')/+!ꢀHBꢀZ"\ꢀC3#=9#,A",!3#ꢀ29:9#29#=9ꢀ3Eꢀ2!EE1G!3#ꢀ=39EE!=!9#,ꢀ(ꢀZC+
c'ꢀROOꢀF8J\ꢀ3EꢀM&mꢀZX\ꢀ<!J9ꢀ2!G,A!X1,!3#Gꢀ3EꢀM&ꢀ",ꢀ2!EE9A9#,ꢀ=3#=9#,A",!3#Gꢀ3EꢀaSNC`ꢀ1#!,Gꢀ!#ꢀ,%9ꢀ
H!],1A9ꢀ3EꢀC8C4hC8CDꢀZNhN'ꢀ&)&\mꢀZ=\ꢀ*wꢀ"#2ꢀ*wwꢀL9AG1Gꢀ+ꢀE3Aꢀ,%9ꢀ&9DꢀW!,%ꢀ,%9ꢀ=3#=9#,A",!3#ꢀ3Eꢀ
aSNC`ꢀ1#!,ꢀ3EꢀSROꢀHFꢀ!#ꢀC8C4hC8CDꢀZNhN'ꢀ&)&\mꢀZ2\ꢀ<IFꢀ!H"&9ꢀ3EꢀM&ꢀW!,%ꢀ,%9ꢀ=3#=9#,A",!3#ꢀ
3EꢀaSNC`ꢀ1#!,ꢀ3EꢀNOꢀHFꢀ!#ꢀC8C4hC8CDꢀZNhN'ꢀ&)&\Bꢀ-%9ꢀG="D9ꢀX"Aꢀ!GꢀNꢀxHB
M S S
C4hC+CDꢀnꢀNhN'ꢀ&)&'ꢀSeQꢀ
M
S
S
M
S
S
M
S
S
dꢀ
-
%9ꢀG1:A"H3D9=1D"Aꢀ&9Dꢀ9]%!X!,92ꢀ&9DYG3Dꢀ,A"#G!,!3#Gꢀ,A!&&9A92ꢀX;ꢀ,%9AH3'ꢀc "#2ꢀ
N'R'`'NOY,9,A""J"=;=D32329="#9ꢀZ=;=D9#\ꢀZV!&1A9ꢀQ\BꢀK:3#ꢀ%9",!#&ꢀ3Aꢀ,%9ꢀ"22!,!3#ꢀ3Eꢀ
d
c'ꢀ,%9ꢀ&9Dꢀ,1A#92ꢀ!#,3ꢀG3D1,!3#ꢀ219ꢀ,3ꢀ,%9ꢀ29G,A1=,!3#ꢀ3Eꢀ,%9ꢀaSNC`hG9=3#2"A;ꢀ
"HH3#!1HꢀG"D,ꢀ!#,9A"=,!3#GBꢀ-%9ꢀ"22!,!3#ꢀ3Eꢀ=;=D9#ꢀ=31D2ꢀW9"T9#ꢀ,%9ꢀ=33A2!#",!3#ꢀ
Sd
X9,W99#ꢀ$# ꢀ"#2ꢀ,9A:;A!2;Dꢀ&A31:G'ꢀ"==3H:"#!92ꢀW!,%ꢀ,%9ꢀ29&A"2",!3#ꢀ3Eꢀ,%9ꢀ&9D'ꢀ
W%!=%ꢀW"Gꢀ9L!29#=92ꢀX;ꢀ,%9ꢀ,!,A",!3#ꢀKiYi!Gꢀ"XG3A:,!3#ꢀ"GꢀG%3W#ꢀ!#ꢀV!&1A9ꢀ<RUBꢀ
Sd
g!,%ꢀ,%9ꢀ=3#,!#131Gꢀ"22!,!3#ꢀ3Eꢀ=;=D9#'ꢀ,%9ꢀ"XG3AX"#=9ꢀ3Eꢀ,%9ꢀ$# h,9A:;A!2;DꢀX"#2ꢀ",ꢀ
MeSꢀ#Hꢀ29=A9"G92Bꢀꢁ22!#&ꢀNBSꢀ9k1!LBꢀ3Eꢀ=;=D9#ꢀA9G1D,92ꢀ!#ꢀ,%9ꢀ,3,"Dꢀ2!G"::9"A"#=9ꢀ3Eꢀ
Sd
$# h,9A:;A!2;Dꢀ "XG3A:,!3#ꢀ X"#2GBꢀ ꢁE,9Aꢀ E1A,%9Aꢀ "22!,!3#ꢀ 3Eꢀ 9k1"Dꢀ "H31#,Gꢀ 3Eꢀ
$#Zl-E\'ꢀ,%9ꢀ"XG3A:,!3#ꢀX"#2ꢀ",ꢀMeSꢀA9"::9"A92Bꢀ-%9ꢀ&9Dꢀ=31D2ꢀX9ꢀA9E3AH92ꢀ1:3#ꢀ
S
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 12 of 19
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
ACS Paragon Plus Environment

Page 13 of 19
Journal of the American Chemical Society
1
2
3
4
5
6
7
8
9
2
9G,A3;92ꢀZV!&1A9ꢀ`"\Bꢀ-%9#ꢀ,%9ꢀ&9DꢀW"GꢀG,12!92ꢀ1#29AꢀD"A&9ꢀZROOy\ꢀ"#2ꢀGH"DDꢀZOBNy\ꢀ
G,A"!#G'ꢀA9G:9=,!L9D;BꢀꢁGꢀG%3W#ꢀ!#ꢀV!&1A9ꢀ`X'ꢀ!#!,!"DD;'ꢀW%9#ꢀ,%9ꢀG,A"!#ꢀW"GꢀROOy'ꢀ*vꢀ
W"GꢀD"A&9Aꢀ,%"#ꢀ*u'ꢀ!#2!=",!#&ꢀ,%",ꢀ,%9ꢀ&9DꢀW"GꢀXA3T9#Bꢀ<1XG9k19#,D;'ꢀ,%9ꢀG,A"!#ꢀW"Gꢀ
A9D9"G92ꢀ,3ꢀOBNyꢀ"#2ꢀ,%9ꢀ&9DꢀW"GꢀD9E,ꢀG,"#2!#&ꢀE3AꢀPOꢀG'ꢀ"#2ꢀX3,%ꢀ*uꢀ"#2ꢀ*vꢀA9,1A#92ꢀ,3ꢀ
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
,
,
%9!Aꢀ3A!&!#"DꢀL"D19GBꢀ-%!Gꢀ:A3=9GGꢀ=31D2ꢀX9ꢀA9:9",92ꢀE3AꢀE31Aꢀ,!H9GꢀW!,%31,ꢀ"#;ꢀD3GGꢀ3Eꢀ
%9ꢀH321D1GBꢀ-%9G9ꢀ3XG9AL",!3#Gꢀ!#2!=",9ꢀ,%",ꢀ,%9ꢀ&9Dꢀ:3GG9GG9Gꢀ&332ꢀG9DEY%9"D!#&ꢀ
:
A3:9A,!9GB
'
#
'
"
&
!
%
I&J%
I6J%
(
ꢀ())
)
()
ꢀ())
%
"
%
%
%
%
%
&
%
!
%
!
"
#
$
%
%!
%"
%#
%
%
./01ꢀ+ꢀ2
345-/6ꢀ+ꢀ7
F')/+!ꢀLBꢀZ"\ꢀ*wꢀ"#2ꢀ*wwꢀL9AG1GꢀG,A"!#ꢀGW99:BꢀZX\ꢀz9Dꢀ!#ꢀ=3#,!#131GꢀG,9:YG,A"!#ꢀH9"G1A9H9#,GBꢀ-%9ꢀ
9DꢀW!,%ꢀ,%9ꢀ=3#=9#,A",!3#ꢀ3EꢀaSNC`ꢀ1#!,ꢀ3EꢀSROꢀHFꢀ!#ꢀC8C4hC8CDꢀZNhN'ꢀ&)&\ꢀW"GꢀG1X/9=,92ꢀ,3ꢀ
ROOyꢀG,A"!#ꢀE3AꢀPOꢀG'ꢀ,%9#ꢀX"=Tꢀ,3ꢀOBNyꢀG,A"!#ꢀ"#2ꢀA9,"!#92ꢀE3AꢀPOꢀG'ꢀ!#ꢀ,%9ꢀD!#9"AꢀA9&!H9ꢀE3AꢀMOOꢀG'ꢀ
&
M
S
S
"
#2ꢀE31Aꢀ=;=D9GꢀW9A9ꢀ23#9B
-
%9ꢀ3:,!="Dꢀ:A3:9A,!9Gꢀ3Eꢀ,%9ꢀD!&"#2G'ꢀH9,"DD"=;=D9G'ꢀD!#9"AꢀG1:A"H3D9=1D"Aꢀ
:
3D;H9AGꢀ"#2ꢀ,%9ꢀ=A3GGYD!#T92ꢀG1:A"H3D9=1D"Aꢀ:3D;H9AGꢀW9A9ꢀG,12!92ꢀX;ꢀKiYi!Gꢀ
"
XG3A:,!3#ꢀ"#2ꢀED13A9G=9#=9ꢀG:9=,A3G=3:;ꢀ"GꢀG%3W#ꢀ!#ꢀV!&1A9ꢀUꢀ"#2ꢀV!&1A9ꢀ<Re'ꢀ"#2ꢀ
,
%9ꢀ3:,!="Dꢀ2","ꢀ"A9ꢀG1HH"A!J92ꢀ!#ꢀ-"XD9ꢀ<NBꢀVA3HꢀV!&1A9ꢀU'ꢀ,%9ꢀ"XG3A:,!3#ꢀ"#2ꢀ
9H!GG!3#ꢀ H"]!H"ꢀ 3Eꢀ ,%9ꢀ H9,"DD"=;=D9Gꢀ A92G%!E,ꢀ W!,%ꢀ ,%9ꢀ !#=A9"G9ꢀ 3Eꢀ ,%9ꢀ
9D9=,A3#Y23#",!#&ꢀ"X!D!,;ꢀ3Eꢀ,%9ꢀG1XG,!,19#,Gꢀ",,"=%92ꢀ,3ꢀ,%9ꢀ:;A!2;DꢀD!&"#2GBꢀ43,"XD;'ꢀ
E&ꢀW!,%ꢀ"H!#3ꢀG1XG,!,19#,Gꢀ9]%!X!,GꢀXA3"2ꢀ9H!GG!3#ꢀEA3HꢀROOꢀ,3ꢀ`QOꢀ#HBꢀ-%9ꢀ
ED13A9G=9#=9ꢀG:9=,A"ꢀH"]!H"ꢀ3Eꢀ,%9ꢀD!#9"AꢀG1:A"H3D9=1D"Aꢀ:3D;H9AGꢀH&ꢀZQMeꢀ#H\ꢀ"#2ꢀ
H6ꢀ ZR`Mꢀ #H\ꢀ "A9ꢀ D"A&9D;ꢀ A92G%!E,92ꢀ A9D",!L9ꢀ ,3ꢀ ,%3G9ꢀ 3Eꢀ ,%9!Aꢀ =3AA9G:3#2!#&ꢀ
H9,"DD"=;=D9GꢀE&ꢀZRRUꢀ#H\ꢀ"#2ꢀE6ꢀZRMOꢀ#H\'ꢀA9G:9=,!L9D;'ꢀW%!=%ꢀ="#ꢀX9ꢀ",,A!X1,92ꢀ,3ꢀ
,%9ꢀ 9],9#292ꢀ =3#/1&",!3#ꢀ "A!G!#&ꢀ EA3Hꢀ ,%9ꢀ J!#=Y,9A:;A!2!#9ꢀ =33A2!#",!3#Bꢀ -%9ꢀ
=A3GGYD!#T92ꢀG1:A"H3D9=1D"Aꢀ:3D;H9AGꢀ9]%!X!,ꢀ9H!GG!3#ꢀW"L9D9#&,%GꢀG!H!D"Aꢀ,3ꢀ,%3G9ꢀ
"
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 14 of 19
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
ACS Paragon Plus Environment

Page 15 of 19
Journal of the American Chemical Society
1
2
3
4
5
6
7
8
9
G1:A"H3D9=1D"Aꢀ:3D;H9AGꢀW!,%ꢀ!#,9A9G,!#&ꢀ"#2ꢀ1G9E1Dꢀ=%"A"=,9A!G,!=GB
A
94:A8B?ꢀ49>8B>8
00,+*'()ꢀ:(#,+-&*',(
/
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
-%9ꢀ<1::3A,!#&ꢀ[#E3AH",!3#ꢀ!Gꢀ"L"!D"XD9ꢀEA99ꢀ3Eꢀ=%"A&9ꢀ3#ꢀ,%9ꢀꢁC<ꢀ@1XD!=",!3#Gꢀ
W9XG!,9ꢀ",ꢀ+l[q
<
;#,%9G!G'ꢀ4F0'ꢀI<[Y-lVYF<'ꢀ<IF'ꢀ"#2ꢀKiYi!Gꢀ2","B
A@8%9=ꢀ:>F9=OA8:9>
,++!30,(5'()ꢀA/*7,+3
4
?
;!#G={%J#1B921B=#
?
G,"#&{=%9HB1,"%B921
A/*7,+ꢀ4,(*+'6/*',(3
*
B$Bꢀ"#2ꢀ+B-Bꢀ=3#,A!X1,92ꢀ9k1"DD;ꢀ,3ꢀ,%!GꢀW3ATB
>,*!3
-
%9A9ꢀ"A9ꢀ#3ꢀ=3#ED!=,Gꢀ,3ꢀ29=D"A9B
A4P>9QCB?ROB>8
B>Bꢀ,%"#TGꢀ4",!3#"Dꢀ4",1A"Dꢀ<=!9#=9ꢀV31#2",!3#ꢀ3EꢀC%!#"ꢀZSNe`NOReꢀ"#2ꢀSNQ`ROMR\ꢀ
<
"#2ꢀ $%9/!"#&ꢀ @A3L!#=!"Dꢀ 4",1A"Dꢀ <=!9#=9ꢀ V31#2",!3#ꢀ 3Eꢀ C%!#"ꢀ Z$.4<V\ꢀ
Z6 NUaOROOONꢀ"#2ꢀ6>NPaOROOOP\ꢀE3AꢀE!#"#=!"DꢀG1::3A,Bꢀ B$Bꢀ,%"#TGꢀ4",!3#"Dꢀ
4",1A"Dꢀ<=!9#=9ꢀV31#2",!3#ꢀ3EꢀC%!#"ꢀZQN`OMORP\ꢀ"#2ꢀC%!#"ꢀ<=%3D"AG%!:ꢀC31#=!DꢀE3Aꢀ
E!#"#=!"DꢀG1::3A,Bꢀ@B.B<Bꢀ,%"#TGꢀ4[8ꢀZzA"#,ꢀ0ONYCꢁSNQNQ`\ꢀE3AꢀE!#"#=!"DꢀG1::3A,B
=BFB=B>4B
ZN\ꢀC3A2!9A'ꢀ@Bmꢀ-31A#!D%"='ꢀVBmꢀ<31D!|Y$!"T3L!='ꢀCBmꢀ69!XD9A'ꢀ6Bꢀ<9DEY89"D!#&ꢀ"#2ꢀ-%9AH3A9L9AG!XD9ꢀ
0
1XX9AꢀEA3Hꢀ<1:A"H3D9=1D"AꢀꢁGG9HXD;Bꢀ,!-./0ꢀDSSN'ꢀ123'ꢀe``B
ZS\ꢀ29ꢀzA99E'ꢀ-BꢀVBꢀꢁBmꢀF9!/9A'ꢀIBꢀgBꢀ<1:A"H3D9=1D"Aꢀ@3D;H9AGBꢀ,!-./0ꢀDSSN'ꢀ124'ꢀN`NB
ZM\ꢀ<"#&99,%"'ꢀ4BꢀFBmꢀF"!,A"'ꢀKBꢀ<1:A"H3D9=1D"Aꢀz9DGqꢀV1#=,!3#Gꢀ"#2ꢀKG9GBꢀ560$7ꢀ89:7ꢀ;0&7ꢀDSSK'ꢀ41'ꢀ
USNB
ZR\ꢀ<1#'ꢀ.Bꢀ>Bmꢀ$%"3'ꢀ7Bmꢀ[DD9:9A1H"'ꢀgBꢀ0BꢀcBmꢀC%"12%1A!'ꢀlBmꢀl%'ꢀcBꢀ8BmꢀF33#9;'ꢀ+Bꢀ.BmꢀiD"GG"T'ꢀ.Bꢀ.Bmꢀ
<13'ꢀ$Bꢀ8!&%D;ꢀ<,A9,=%"XD9ꢀ"#2ꢀ-31&%ꢀ8;2A3&9DGBꢀ,!-./0ꢀDSꢁD'ꢀ1<='ꢀNMMB
ZQ\ꢀ$%"#&'ꢀ>Bꢀ<Bmꢀc%"29H%3GG9!#!'ꢀꢁBꢀꢁ2L"#=9Gꢀ!#ꢀI#&!#99A!#&ꢀ8;2A3&9DGBꢀ8:>0?:0ꢀDSꢁL'ꢀ42@'ꢀMPS`B
ZP\ꢀc"T1,"'ꢀ-Bmꢀ>"H"&!G%!'ꢀ-Bmꢀl&3G%!'ꢀ-Bꢀ<,!H1D!Y09G:3#G!L9ꢀ<1:A"H3D9=1D"AꢀꢁGG9HXD!9GꢀC3#G,A1=,92ꢀ
$
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 16 of 19
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
EA3Hꢀ@!DD"Ao?p"A9#9GBꢀA::7ꢀ560$7ꢀ;0ꢁ7ꢀDSꢁN'ꢀ23'ꢀNPQPB
Z`\ꢀa1A#W3A,%'ꢀFBmꢀ-"#&'ꢀ6Bmꢀc1H:E9A'ꢀ.Bꢀ0Bmꢀ+1#="#'ꢀꢁBꢀ.Bmꢀa9;9A'ꢀVBꢀ6BmꢀV!3A9'ꢀzBꢀ6Bmꢀ03W"#'ꢀ<Bꢀ.Bmꢀ
g929A'ꢀCBꢀl:,!="DD;ꢀ89"D"XD9ꢀ<1:A"H3D9=1D"Aꢀ@3D;H9AGBꢀ,!-./0ꢀDSꢁꢁ'ꢀ1BC'ꢀMMRB
ZU\ꢀ>"#&'ꢀ>BmꢀKAX"#'ꢀFBꢀgBꢀ<9DEY89"D!#&ꢀ@3D;H9A!=ꢀF",9A!"DGBꢀ560$7ꢀ89:7ꢀ;0&7ꢀDSꢁE'ꢀ1C'ꢀ`RRPB
Ze\ꢀ !#'ꢀaBmꢀ$%"#&'ꢀ<Bmꢀ<3#&'ꢀ Bmꢀ81"#&'ꢀ$Bmꢀ71'ꢀ.BꢀVBmꢀ$%"#&'ꢀ7Bꢀ<1:A"H3D9=1D"Aꢀ[#,9AE"=!"Dꢀ
@3D;H9A!J",!3#qꢀꢁꢀC3#,A3DD"XD9ꢀF9,%32ꢀ3EꢀV"XA!=",!#&ꢀ<1:A"H3D9=1D"Aꢀ@3D;H9A!=ꢀF",9A!"DGBꢀA?D0E7ꢀ
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
5
60$7ꢀF?-7ꢀG >-7ꢀDSꢁL'ꢀ2@'ꢀ`PMeB
ZNO\ꢀ<,1"A,'ꢀFBꢀꢁBꢀCBmꢀ81=T'ꢀgBꢀ-Bꢀ<Bmꢀz9#J9A'ꢀ.BmꢀF}DD9A'ꢀFBmꢀlX9A'ꢀCBmꢀ<,"HH'ꢀFBmꢀ<1T%3A1T3L'ꢀzBꢀ
aBmꢀ<JD9!E9A'ꢀ[Bmꢀ-G1TA1T'ꢀiBꢀiBmꢀKAX"#'ꢀFBmꢀg!##!T'ꢀVBmꢀ$"1G=%9A'ꢀ<Bmꢀ61J!#3L'ꢀ[BmꢀF!#T3'ꢀ<BꢀIH9A&!#&ꢀ
ꢁ::D!=",!3#Gꢀ3Eꢀ<,!H1D!Y09G:3#G!L9ꢀ@3D;H9AꢀF",9A!"DGBꢀ,!-7ꢀH!-0/7ꢀDSꢁS'ꢀ='ꢀNONB
ZNN\ꢀ>1'ꢀzBꢀCBmꢀ$%"3'ꢀ7Bꢀ6Bmꢀ$%31'ꢀ.BmꢀF"3'ꢀ$BꢀgBmꢀ81"#&'ꢀ7Bꢀ6Bmꢀg"#&'ꢀ$Bꢀ-Bmꢀ81"'ꢀaBmꢀ6!1'ꢀ>Bꢀ.Bmꢀ
$
%"#&'ꢀVBꢀgBmꢀ89'ꢀ$BꢀFBmꢀ."=3XG3#'ꢀlBmꢀz"3'ꢀCBꢀ>Bmꢀg"#&'ꢀgBꢀ6Bmꢀ>1'ꢀCBꢀ>Bmꢀ$%1'ꢀ7Bꢀ>Bmꢀ81"#&'ꢀVBꢀ8Bmꢀ
C%9#'ꢀ7Bꢀ>Bꢀ <1:A"H3D9=1D"Aꢀ@3D;H9AYa"G92ꢀ4"#3H92!=!#9qꢀ8!&%ꢀ-%9A":91,!=ꢀ@9AE3AH"#=9ꢀ"#2ꢀ
49&D!&!XD9ꢀ63#&Y-9AHꢀ[HH1#3,3]!=!,;Bꢀ#7ꢀA$7ꢀ560$7ꢀ89:7ꢀDSꢁN'ꢀ31I'ꢀUOOQB
ZNS\ꢀ>"#'ꢀ7Bꢀ$Bmꢀ6!1'ꢀ$Bꢀ>Bmꢀ$%"#&'ꢀ Bꢀ8Bmꢀ63:9J'ꢀ.Bmꢀg"#&'ꢀ8Bmꢀg1'ꢀ8BꢀCBmꢀ4!1'ꢀ<BꢀFBmꢀ>"#'ꢀ8Bꢀ@Bmꢀ
g"#&'ꢀ<Bꢀ8Bmꢀ69!'ꢀ-Bmꢀ6!'ꢀ.Bꢀ8Bmꢀ !'ꢀ+Bꢀ@Bmꢀ81"#&'ꢀ@BꢀzBmꢀ81"#&'ꢀ.Bꢀ@Bmꢀ$%"#&'ꢀ>Bmꢀg"#&'ꢀ>Bꢀ>Bmꢀ6!'ꢀzBꢀ6Bmꢀ
-
3T'ꢀ.BꢀaBꢀ8BmꢀC%9#'ꢀ7Bꢀ+Bmꢀa"3'ꢀ$Bꢀ4Bꢀ 1"2A1:D9ꢀ8Ya3#2!#&ꢀCA3GGY6!#T92ꢀ<1:A"H3D9=1D"Aꢀ@3D;H9A!=ꢀ
F",9A!"DGꢀ"Gꢀ<1XG,A",9GꢀE3Aꢀ<,A9,=%"XD9'ꢀꢁ#,!,9"A!#&'ꢀ"#2ꢀ<9DEY89"D"XD9ꢀ-%!#ꢀV!DHꢀID9=,A329GBꢀ#7ꢀA$7ꢀ
560$7ꢀ89:7ꢀDSꢁN'ꢀ31I'ꢀQSUOB
ZNM\ꢀF"'ꢀCBmꢀ61'ꢀgBmꢀ>"#&'ꢀ7Bmꢀ89'ꢀ.Bmꢀ69'ꢀ7Bmꢀg"#&'ꢀ6Bmꢀ$%"#&'ꢀ.Bmꢀ<9A:9'ꢀFBꢀ.Bmꢀ81"#&'ꢀ>BmꢀC%9#'ꢀ-Bꢀ
a!3!#G:!A92ꢀ ꢁ#!G3,A3:!=ꢀ 8;2A3&9Dꢀ ꢁ=,1",3AGꢀ W!,%ꢀ l#!lEEꢀ <W!,=%"XD9ꢀ "#2ꢀ C3D3A "-1#"XD9ꢀ
VD13A9G=9#=9ꢀa9%"L!3AGBꢀA &7ꢀJ.?:-7ꢀH!-0/7ꢀDSꢁN'ꢀC<'ꢀN`ORQPUB
ZNR\ꢀC1!'ꢀ>Bꢀ8Bmꢀ+9#&'ꢀ0Bmꢀ6!'ꢀ$Bmꢀ+1'ꢀ7Bꢀ<Bmꢀ.!"'ꢀ Bmꢀg"#&'ꢀ7Bꢀ8Bmꢀg"#&'ꢀCBꢀ>BmꢀF9&19DD",!'ꢀcBmꢀ>"#&'ꢀ
>BꢀgBꢀ@!DD"AoQpꢁA9#9ꢀ@G9123oNp03,"]"#9Ya"G92ꢀ0923]Y09G:3#G!L9ꢀ<1:A"H3D9=1D"Aꢀi9G!=D9GꢀE3Aꢀ
C3#,A3DD92ꢀ+A1&ꢀ09D9"G9BꢀH!-0/7ꢀ560$7ꢀJ/9?-7ꢀDSꢁT'ꢀ4'ꢀNRS`B
ZNQ\ꢀ>!#'ꢀ$Bmꢀ<3#&'ꢀzBmꢀ.!"3'ꢀ>Bmꢀ$%9#&'ꢀ@Bmꢀ71'ꢀ.BꢀVBmꢀ$%"#&'ꢀ7Bꢀ+!GG!:",!L9ꢀ<1:A"H3D9=1D"Aꢀ
@3D;H9A!J",!3#ꢀ@3W9A92ꢀX;ꢀ6!&%,Bꢀ558ꢀ560$7ꢀDSꢁTKꢀ3KꢀMMQ7
ZNP\ꢀ6!'ꢀaBmꢀ89'ꢀ-BmꢀV"#'ꢀ>Bmꢀ>1"#'ꢀ7Bmꢀ !1'ꢀ8Bmꢀ>!#'ꢀ<Bꢀ09=9#,ꢀ+9L9D3:H9#,Gꢀ!#ꢀ,%9ꢀC3#G,A1=,!3#ꢀ3Eꢀ
F9,"DD"=;=D9hF9,"DD"="&9YC3A92ꢀ<1:A"H3D9=1D"Aꢀ@3D;H9AGꢀL!"ꢀ8!9A"A=%!="Dꢀ<9DEYꢁGG9HXD;Bꢀ560$7ꢀ
5
9$$.?7ꢀDSꢁT'ꢀ22'ꢀUOMPB
ZN`\ꢀ6!'ꢀaBmꢀ89'ꢀ-Bmꢀ<%9#'ꢀ7Bmꢀ-"#&'ꢀ+Bmꢀ>!#'ꢀ<BꢀVD13A9G=9#,ꢀ<1:A"H3D9=1D"Aꢀ@3D;H9AGꢀW!,%ꢀꢁ&&A9&",!3#ꢀ
[#21=92ꢀIH!GG!3#ꢀ@A3:9A,!9GBꢀL9MN$7ꢀ560$7ꢀDSꢁT'ꢀ3I'ꢀ`ePB
ZNU\ꢀ>"#'ꢀ7Bꢀ$Bmꢀg"#&'ꢀVBmꢀ$%9#&'ꢀaBmꢀ81"#&'ꢀVBꢀ8Bꢀ<,!H1D!Y09G:3#G!L9ꢀ<1:A"H3D9=1D"Aꢀ@3D;H9A!=ꢀ
F",9A!"DGBꢀ560$7ꢀ89:7ꢀ;0&7ꢀDSꢁD'ꢀ13'ꢀPORSB
ZNe\ꢀa9=T'ꢀ.BꢀaBmꢀ03W"#'ꢀ<Bꢀ.BꢀF1D,!G,!H1D!'ꢀF1D,!A9G:3#G!L9ꢀF9,"DD3Y<1:A"H3D9=1D"Aꢀ@3D;H9AGBꢀ#7ꢀA$7ꢀ
5
60$7ꢀ89:7ꢀDSSE'ꢀ3C2'ꢀNMeSSB
ZSO\ꢀ<=%H",D3=%'ꢀ<Bmꢀz3#J"D9J'ꢀFBꢀVBmꢀ<=%1X9A,'ꢀKBꢀ<BꢀF9,"DD3Y<1:A"H3D9=1D"Aꢀ+!9,%;D9#9ꢀzD;=3Dqꢀ
g",9AY<3D1XD9ꢀ09L9AG!XD9ꢀ@3D;H9AGBꢀH!:/9$9M7ꢀ;!O> ꢀ59$$.?7ꢀDSSD'ꢀC4'ꢀeQ`B
ZSN\ꢀF9!'ꢀ.BꢀVBmꢀ.!"'ꢀ7Bꢀ>Bmꢀ6"!'ꢀ.BꢀCBmꢀ<1#'ꢀ>Bmꢀ6!'ꢀCBꢀ8Bmꢀg1'ꢀ.Bꢀ8BmꢀC"3'ꢀ>Bmꢀ>31'ꢀ7Bꢀ$Bmꢀa"3'ꢀ$Bꢀ4Bꢀꢁꢀ
8!&%D;ꢀ<,A9,=%"XD9ꢀ"#2ꢀꢁ1,3#3H31Gꢀ<9DEY89"D!#&ꢀ@3D;H9Aꢀa"G92ꢀ3#ꢀC3HX!#",!3#ꢀ3Eꢀ@,~~~@,ꢀ"#2ꢀf^fꢀ
[#,9A"=,!3#GBꢀH!:/9$9M7ꢀ;!O> ꢀ59$$.?7ꢀDSꢁM'ꢀ4B'ꢀNPP`B
ZSS\ꢀ<=%1X9A,'ꢀKBꢀ<BmꢀIG=%X"1H9A'ꢀCBꢀF"=A3H3D9=1D9GꢀC3#,"!#!#&ꢀa!:;A!2!#9ꢀ"#2ꢀ-9A:;A!2!#9ꢀF9,"Dꢀ
C3H:D9]9Gqꢀ-3W"A2GꢀF9,"DD3G1:A"H3D9=1D"Aꢀ@3D;H9AGBꢀA?D0E7ꢀ560$7ꢀF?-7ꢀG >-7ꢀDSSD'ꢀ13'ꢀSUeSB
ZSM\ꢀ831G9=A3E,'ꢀCBꢀIBꢀR'SuqPu'RuuY-9A:;A!2!#9Gqꢀ+!L9A&!#&ꢀ"#2ꢀ+!L9AG9ꢀa1!D2!#&ꢀaD3=TGꢀ!#ꢀC33A2!#",!3#ꢀ
%
ACS Paragon Plus Environment

Page 17 of 19
Journal of the American Chemical Society
1
2
3
4
5
6
7
8
9
@3D;H9AGꢀ"#2ꢀF9,"DD3H"=A3=;=D9GBꢀ(!M-9?ꢀP/!?ꢁ7ꢀDSꢁH'ꢀ14'ꢀPQeRB
ZSR\ꢀzAÄ&9A'ꢀzBmꢀF9;9AY$"!T"'ꢀgBmꢀaÄ,,=%9A'ꢀCBmꢀzAÄ%#'ꢀVBmꢀ01,%"A2'ꢀCBmꢀ<=%H1=T'ꢀCBꢀ<W!,=%"XD9ꢀ
<1:A"H3D9=1D"Aꢀ@3D;H9AGꢀEA3Hꢀ,%9ꢀ<9DEYꢁGG9HXD;ꢀ3Eꢀ"ꢀ<H"DDꢀF3#3H9AꢀW!,%ꢀ-W3ꢀlA,%3&3#"Dꢀa!#2!#&ꢀ
[#,9A"=,!3#GBꢀ#7ꢀA$7ꢀ560$7ꢀ89:7ꢀDSꢁꢁ'ꢀ344'ꢀUePNB
ZSQ\ꢀ699'ꢀ>Bꢀ8Bmꢀ89'ꢀ6Bꢀ@BmꢀC%"#'ꢀ>Bꢀ-Bꢀ<,!H1D!Y09G:3#G!L9ꢀ<1:A"H3D9=1D"Aꢀz9DGꢀC3#G,A1=,92ꢀX;ꢀ
8!9A"A=%!="Dꢀ<9DEYꢁGG9HXD;ꢀa"G92ꢀ3#ꢀF9,"DY6!&"#2ꢀC33A2!#",!3#ꢀ"#2ꢀ83G,Yz19G,ꢀ09=3&#!,!3#Bꢀ
H!:/9$9M7ꢀ;!O> ꢀ59$$.?7ꢀDSꢁN'ꢀ4='ꢀPB
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
ZSP\ꢀ6!'ꢀ6Bꢀ.BmꢀC3#&'ꢀ>Bmꢀ89'ꢀ6Bꢀ@Bmꢀg"#&'ꢀ>Bꢀ>Bmꢀg"#&'ꢀ.Bmꢀ$%"#&'ꢀVBꢀFBmꢀa1'ꢀgBꢀVBꢀF1D,!:D9ꢀ
<,!H1D!Y09G:3#G!L9ꢀ<1:A"H3D9=1D"Aꢀz9DGꢀC3#G,A1=,92ꢀEA3HꢀF9,"DYlA&"#!=ꢀC;=D9GBꢀL9MN$7ꢀ 560$7ꢀ
DSꢁM'ꢀB'ꢀPSUUB
ZS`\ꢀzÄ,J'ꢀ<BmꢀꢁX9#2'ꢀFBmꢀ$9=%9D'ꢀ<Bmꢀ8"&9A'ꢀFBꢀ+Bmꢀ<=%1X9A,'ꢀKBꢀ<Bꢀ@D",!#1HY-9A:;A!2!#9ꢀC3H:D9]9Gꢀ
!
#ꢀ@3D;H9AGqꢀꢁꢀ43L9Dꢀꢁ::A3"=%ꢀE3Aꢀ,%9ꢀ<;#,%9G!Gꢀ3Eꢀ<9DEY89"D!#&ꢀF9,"DD3:3D;H9AGBꢀ#7ꢀAOOM7ꢀL9MN$7ꢀ
:>7ꢀDSꢁT'ꢀ34@'ꢀR`OPRB
8
ZSU\ꢀ$%9#&'ꢀ BmꢀF"'ꢀ$Bmꢀz3#&'ꢀ<BꢀF1D,!Y<,!H1D!Y09G:3#G!L9ꢀ<9DEY89"D!#&ꢀF9,"DD3G1:A"H3D9=1D"Aꢀ
@3D;H9Aꢀ4"#3=3H:3G!,9GBꢀ#7ꢀH!-0/7ꢀ560$7ꢀA'ꢀDSꢁM'ꢀ1'ꢀMMSRB
ZSe\ꢀC33T'ꢀ-Bꢀ0Bmꢀ<,"#&'ꢀ@Bꢀ.Bꢀ09=9#,ꢀ+9L9D3:H9#,Gꢀ!#ꢀ,%9ꢀ@A9:"A",!3#ꢀ"#2ꢀC%9H!G,A;ꢀ3EꢀF9,"DD"=;=D9Gꢀ
"
#2ꢀF9,"DD"="&9GꢀL!"ꢀC33A2!#",!3#Bꢀ560$7ꢀ;0&7ꢀDSꢁK'ꢀ332'ꢀ`OONB
ZMO\ꢀV1/!,"'ꢀFBmꢀ-3H!#"&"'ꢀFBmꢀ83A!'ꢀꢁBmꢀ-%9AA!9#'ꢀaBꢀC33A2!#",!3#ꢀꢁGG9HXD!9GꢀEA3Hꢀ"ꢀ@2Z[[\YC3A#9A92ꢀ
<k1"A9ꢀC3H:D9]BꢀA::7ꢀ560$7ꢀ;0ꢁ7ꢀDSSK'ꢀ4<'ꢀMPeB
ZMN\ꢀ<=%H!,,'ꢀVBmꢀVA9129#A9!=%'ꢀ.Bmꢀa"AA;'ꢀ4Bꢀ@BꢀIBmꢀ.1!DD9A",Y.9"##9A9,'ꢀ6Bmꢀ<}GGYV!#T'ꢀzBmꢀ-%9AA!9#'ꢀaBꢀ
lA&"#3H9,"DD!=ꢀC"&9Gꢀ"Gꢀi9%!=D9GꢀE3Aꢀ[#,A"=9DD1D"Aꢀ09D9"G9ꢀ3Eꢀ@%3,3G9#G!,!J9AGBꢀ#7ꢀA$7ꢀ560$7ꢀ89:7ꢀ
DSꢁD'ꢀ341'ꢀ`QRB
S R R U
ZMS\ꢀCD9L9A'ꢀzBꢀ8Bmꢀ@1#,'ꢀ@BꢀC",!3#^ꢁ#!3#ꢀꢁAA"#&9H9#,ꢀ@",,9A#Gꢀ!#ꢀ<9DEYꢁGG9HXD92ꢀ@26ꢀ"#2ꢀ@26ꢀ
C33A2!#",!3#ꢀC"&9GBꢀA::7ꢀ560$7ꢀ;0ꢁ7ꢀDSꢁL'ꢀ2I'ꢀSSMMB
ZMM\ꢀ$%"3'ꢀCBmꢀ<1#'ꢀ BYVBmꢀ8"A,YC33:9A'ꢀgBꢀFBmꢀ+!@"Gk1"D9'ꢀꢁBꢀzBmꢀ-3G,9'ꢀVBꢀ+Bmꢀa9A&H"#'ꢀ0BꢀzBmꢀ
";H3#2'ꢀcBꢀ4BꢀC%!A"DꢀꢁH!29ꢀ+!A9=,92ꢀꢁGG9HXD;ꢀ3Eꢀ"ꢀ+!"G,9A93Yꢀ"#2ꢀI#"#,!3:1A9ꢀ<1:A"H3D9=1D"Aꢀ
3G,ꢀ"#2ꢀ!,Gꢀꢁ::D!=",!3#ꢀ,3ꢀI#"#,!3G9D9=,!L9ꢀC","D;G!Gꢀ3Eꢀ491,A"Dꢀ<1XG,A",9GBꢀ#7ꢀA$7ꢀ560$7ꢀ89:7ꢀDSꢁE'ꢀ
0
8
342'ꢀNUUOSB
ZMR\ꢀF9#29JYꢁAA3;3'ꢀ.Bmꢀa"AA3G3YVD3A9G'ꢀ.Bmꢀ6!EG=%!,J'ꢀꢁBꢀFBmꢀ<"A/9"#,'ꢀꢁBꢀꢁBmꢀ<,9A#'ꢀCBꢀ6BmꢀF!AT!#'ꢀCBꢀ
ꢁ
BꢀꢁꢀF1D,!Y<,",9'ꢀꢁDD3G,9A!="DD;Y09&1D",92ꢀF3D9=1D"Aꢀ09=9:,3Aꢀg!,%ꢀ<W!,=%"XD9ꢀ<9D9=,!L!,;Bꢀ#7ꢀA$7ꢀ
60$7ꢀ89:7ꢀDSꢁH'ꢀ34@'ꢀNOMROB
ZMQ\ꢀF3Gk19A"'ꢀ.Bmꢀ03#G3#'ꢀ-BꢀcBmꢀ4!,G=%T9'ꢀ.Bꢀ0Bꢀ<1X=3H:3#9#,ꢀVD9]!X!D!,;ꢀI#"XD9GꢀC3#L9AG!3#ꢀ
5
R U U R R
X9,W99#ꢀ( 6 6ꢀꢁGG9HXD!9GBꢀ#7ꢀA$7ꢀ560$7ꢀ89:7ꢀDSꢁM'ꢀ34<'ꢀ
Y<;HH9,A!=ꢀC2[[ ꢀ"#2ꢀPY<;HH9,A!=ꢀC2[[
NUNSB
ZMP\ꢀ<"#"2"'ꢀcBmꢀKX9'ꢀ8Bmꢀ<%!3#3;"'ꢀFBꢀ03,",!3#"DꢀC3#,A3Dꢀ3Eꢀ"ꢀ+!A%32!1HYC9#,9A92ꢀ<1:A"H3D9=1D"Aꢀ
V31AYz9"Aꢀ<;G,9HꢀX;ꢀ6!&"#2ꢀI]=%"#&9Bꢀ#7ꢀA$7ꢀ560$7ꢀ89:7ꢀDSꢁM'ꢀ34<'ꢀSeRQB
ZM`\ꢀ $%"#&'ꢀ $Bmꢀ $%"3'ꢀ $Bmꢀ 831'ꢀ >Bmꢀ g"#&'ꢀ 8Bmꢀ 6!'ꢀ 7Bmꢀ 89'ꢀ zBmꢀ $%"#&'ꢀ FBꢀ ꢁk1931Gꢀ
@D",!#1HZ[[\YC"&9Ya"G92ꢀ 6!&%,Y8"AL9G,!#&ꢀ <;G,9Hꢀ E3Aꢀ @%3,3=","D;,!=ꢀ CA3GGYC31:D!#&ꢀ 8;2A3&9#ꢀ
IL3D1,!3#ꢀ09"=,!3#BꢀA?D0E7ꢀ560$7ꢀF?-7ꢀG >-7ꢀDSꢁT'ꢀ2<'ꢀUUPSB
ZMU\ꢀc!G%!'ꢀ4BmꢀꢁT!,"'ꢀFBmꢀc"H!;"'ꢀFBmꢀ8";"G%!'ꢀ<Bmꢀ8G1'ꢀ8BYVBmꢀ>3G%!J"W"'ꢀFBꢀV"=!D9ꢀC",=%ꢀ"#2ꢀ
09D9"G9ꢀ3EꢀV1DD9A9#9GꢀKG!#&ꢀ"ꢀ@%3,3A9G:3#G!L9ꢀF3D9=1D"Aꢀ-1X9Bꢀ#7ꢀA$7ꢀ560$7ꢀ89:7ꢀDSꢁE'ꢀ342'ꢀNSe`PB
ZMe\ꢀlD!L9A!'ꢀCBꢀzBmꢀz!"##9G=%!'ꢀ4BꢀCBmꢀ4&1;9#'ꢀ<Bꢀ-BmꢀF!AT!#'ꢀCBꢀꢁBmꢀ<,9A#'ꢀCBꢀ6Bmꢀg"WAJ"T'ꢀ$Bmꢀ@!#T'ꢀ
FBꢀ<1:A"H3D9=1D"AꢀꢁDD3G,9A!=ꢀC3E"=!"Dꢀ@3A:%;A!#ꢀC3H:D9]9GBꢀ#7ꢀA$7ꢀ560$7ꢀ89:7ꢀDSSM'ꢀ3C<'ꢀNPSUPB
ZRO\ꢀ71'ꢀ6Bmꢀ<%9#'ꢀ7Bmꢀ$%31'ꢀ$Bmꢀ89'ꢀ-Bmꢀ$%"#&'ꢀ.Bmꢀ !1'ꢀ8Bmꢀ<"%"'ꢀFBꢀ6Bmꢀ>!#'ꢀ<Bmꢀ<,"#&'ꢀ@Bꢀ.Bꢀ
&
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 18 of 19
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
F9,"DD"=;=D9YC3A92ꢀ<1:A"H3D9=1D"Aꢀ@3D;H9AGqꢀVD13A9G=9#=9ꢀ-1#!#&ꢀX;ꢀi"A!",!3#ꢀ3Eꢀ<1XG,!,19#,GBꢀ#7ꢀ
A$7ꢀ560$7ꢀ89:7ꢀDSꢁN'ꢀ31I'ꢀNPeSOB
ZRN\ꢀ$%"#&'ꢀFBmꢀ>!#'ꢀ<Bmꢀ$%"#&'ꢀ.Bmꢀ$%31'ꢀ$Bmꢀ<"%"'ꢀFBꢀ6Bmꢀ61'ꢀCBmꢀ<,"#&'ꢀ@Bꢀ.BꢀF9,"DD"=;=D9YC3A92ꢀ
<1:A"H3D9=1D"AꢀꢁGG9HXD!9GꢀW!,%ꢀ-1#"XD9ꢀVD13A9G=9#=9ꢀ[#=D12!#&ꢀg%!,9Y6!&%,ꢀIH!GG!3#BꢀL/9:7ꢀ,!-M7ꢀ
A:! 7ꢀ8:>7ꢀQ7ꢀ87ꢀA7ꢀDSꢁL'ꢀ331'ꢀMORRB
ZRS\ꢀ$%"#&'ꢀFBmꢀ<"%"'ꢀFBꢀ6Bmꢀg"#&'ꢀFBmꢀ$%31'ꢀ$Bmꢀ<3#&'ꢀaBmꢀ61'ꢀCBmꢀ>"#'ꢀ7Bmꢀ6!'ꢀ7Bmꢀ81"#&'ꢀVBmꢀ>!#'ꢀ
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
<Bmꢀ<,"#&'ꢀ@Bꢀ.BꢀF1D,!=3H:3#9#,ꢀ@D",!#1HZ[[\ꢀC"&9GꢀW!,%ꢀ-1#"XD9ꢀIH!GG!3#ꢀ"#2ꢀꢁH!#3ꢀꢁ=!2ꢀ<9#G!#&Bꢀ
#
7ꢀA$7ꢀ560$7ꢀ89:7ꢀDSꢁL'ꢀ34='ꢀQOP`B
ZRM\ꢀ6!'ꢀ$Bꢀ>Bmꢀ$%"#&'ꢀ>Bmꢀ$%"#&'ꢀCBYgBmꢀC%9#'ꢀ6BY.Bmꢀg"#&'ꢀCBmꢀ-"#'ꢀ8Bmꢀ>1'ꢀ>Bmꢀ6!'ꢀ7Bmꢀ>"#&'ꢀ8BꢀaBꢀ
CA3GGY6!#T92ꢀ <1:A"H3D9=1D"Aꢀ @3D;H9Aꢀ z9DGꢀ C3#G,A1=,92ꢀ EA3Hꢀ +!G=A9,9ꢀ F1D,!Y:!DD"AoQp"A9#9ꢀ
F9,"DD"=;=D9Gꢀ"#2ꢀ-%9!AꢀF1D,!:D9ꢀ<,!H1D!Y09G:3#G!L9ꢀa9%"L!3ABꢀ#7ꢀA$7ꢀ560$7ꢀ89:7ꢀDSꢁH'ꢀ34@'ꢀUQ``B
ZRR\ꢀ<%!'ꢀaBmꢀ6!1'ꢀ>Bmꢀ$%1'ꢀ8Bmꢀi"#29AD!#29#'ꢀ0Bꢀ-Bmꢀ<%"#&&1"#'ꢀ6Bmꢀ4!'ꢀ0Bmꢀꢁ=%"A;;"'ꢀcBmꢀ-"#&'ꢀ.BY8Bmꢀ
$
%31'ꢀ$Bmꢀ6!'ꢀ7Bmꢀ81"#&'ꢀVBmꢀ<,"#&'ꢀ@Bꢀ.Bꢀ<:3#,"#931GꢀV3AH",!3#ꢀ3Eꢀ"ꢀCA3GGY6!#T92ꢀ<1:A"H3D9=1D"Aꢀ
@3D;H9Aꢀa3,%ꢀ!#ꢀ,%9ꢀ<3D!2ꢀ<,",9ꢀ"#2ꢀ!#ꢀ<3D1,!3#'ꢀ+A!L9#ꢀX;ꢀ@D",!#1HZ[[\ꢀF9,"DD"=;=D9Ya"G92ꢀ83G,^
z19G,ꢀ[#,9A"=,!3#GBꢀ#7ꢀA$7ꢀ560$7ꢀ89:7ꢀDSꢁT'ꢀ313'ꢀPReRB
ZRQ\ꢀC%9#'ꢀ6Bꢀ.Bmꢀ>"#&'ꢀ8BꢀaBꢀC3#G,A1=,!3#ꢀ3Eꢀ<,!H1D!Y09G:3#G!L9ꢀV1#=,!3#"DꢀF",9A!"DGꢀL!"ꢀ8!9A"A=%!="Dꢀ
<9DEYꢁGG9HXD;ꢀ[#L3DL!#&ꢀC33A2!#",!3#ꢀ[#,9A"=,!3#GBꢀA::7ꢀ560$7ꢀ;0ꢁ7ꢀDSꢁN'ꢀ23'ꢀSPeeB
ZRP\ꢀ$%9#&'ꢀgBmꢀ>"#&'ꢀzBmꢀ<%"3'ꢀ4Bꢀ4BmꢀC%9#'ꢀ6Bꢀ.Bmꢀl1'ꢀaBmꢀ.!"#&'ꢀ<Bꢀ-BmꢀC%9#'ꢀzBꢀ<Bmꢀ>"#&'ꢀ8BꢀaBꢀCl
S
ꢀ
<,!H1D!Y09G:3#G!L9'ꢀ [#/9=,"XD9ꢀ aD3=Tꢀ C3:3D;H9Aꢀ 8;2A3&9DGꢀ CA3GGY6!#T92ꢀ X;ꢀ +!G=A9,9ꢀ
lA&"#3:D",!#1HZ[[\ꢀF9,"DD"=;=D9GꢀL!"ꢀ<,9:W!G9ꢀ@3G,YꢁGG9HXD;ꢀ@3D;H9A!J",!3#Bꢀ#7ꢀA$7ꢀ560$7ꢀ89:7ꢀ
DSꢁL'ꢀ34='ꢀNMUNNB
ZR`\ꢀ81'ꢀ7BY>Bmꢀ7!"3'ꢀ-Bmꢀ6!#'ꢀCBmꢀ81"#&'ꢀVBmꢀg"#&'ꢀ6Bꢀ +;#"H!=ꢀ<1:A"H3D9=1D"AꢀC3H:D9]9Gꢀ
C3#G,A1=,92ꢀX;ꢀlA,%3&3#"Dꢀ<9DEYꢁGG9HXD;BꢀA::7ꢀ560$7ꢀ;0ꢁ7ꢀDSꢁH'ꢀ1B'ꢀSORNB
ZRU\ꢀ>"#'ꢀ7Bmꢀ6!'ꢀ<BmꢀC33T'ꢀ-Bꢀ0Bmꢀ.!'ꢀ7Bmꢀ>"3'ꢀ>Bmꢀ@3DD3=T'ꢀ.BꢀaBmꢀ<%!'ꢀ>Bmꢀ>1'ꢀzBmꢀ6!'ꢀ.Bmꢀ81"#&'ꢀVBmꢀ
<,"#&'ꢀ @Bꢀ .Bꢀ 8!9A"A=%!="Dꢀ <9DEYꢁGG9HXD;qꢀ g9DDY+9E!#92ꢀ <1:A"H3D9=1D"Aꢀ 4"#3G,A1=,1A9Gꢀ "#2ꢀ
F9,"DD3%;2A3&9DGꢀL!"ꢀꢁH:%!:%!D!=ꢀ+!G=A9,9ꢀlA&"#3:D",!#1HZ[[\ꢀF9,"DD"=;=D9GBꢀ#7ꢀA$7ꢀ560$7ꢀ89:7ꢀ
DSꢁE'ꢀ342'ꢀNROMPB
ZRe\ꢀ>"#'ꢀ7BmꢀC33T'ꢀ-Bꢀ0Bmꢀ@3DD3=T'ꢀ.BꢀaBmꢀg9!'ꢀ@Bmꢀ$%"#&'ꢀ>Bmꢀ>1'ꢀ>Bmꢀ81"#&'ꢀVBmꢀ<,"#&'ꢀ@Bꢀ.Bꢀ
0
9G:3#G!L9ꢀ<1:A"H3D9=1D"Aꢀ@3D;H9AꢀF9,"DD3&9DꢀC3#G,A1=,92ꢀX;ꢀlA,%3&3#"DꢀC33A2!#",!3#Y+A!L9#ꢀ
<9DEYꢁGG9HXD;ꢀ"#2ꢀ83G,hz19G,ꢀ[#,9A"=,!3#GBꢀ#7ꢀA$7ꢀ560$7ꢀ89:7ꢀDSꢁH'ꢀ34@'ꢀRRPOB
ZQO\ꢀ61'ꢀCBmꢀ$%"#&'ꢀFBmꢀ-"#&'ꢀ+Bmꢀ>"#'ꢀ7Bmꢀ$%"#&'ꢀ$Bmꢀ$%31'ꢀ$Bmꢀ<3#&'ꢀaBmꢀg"#&'ꢀ8Bmꢀ6!'ꢀ7Bmꢀ>!#'ꢀ<Bmꢀ
<9:9%A:31A'ꢀ8Bmꢀ<,"#&'ꢀ@Bꢀ.BꢀVD13A9G=9#,ꢀF9,"DD"="&9YC3A9ꢀ<1:A"H3D9=1D"Aꢀ@3D;H9Aꢀz9DꢀV3AH92ꢀX;ꢀ
lA,%3&3#"DꢀF9,"DꢀC33A2!#",!3#ꢀ"#2ꢀ83G,Yz19G,ꢀ[#,9A"=,!3#GBꢀ#7ꢀA$7ꢀ560$7ꢀ89:7ꢀDSꢁN'ꢀ31I'ꢀ`P`RB
ZQN\ꢀ$%31'ꢀ$Bmꢀ>"#'ꢀ7BmꢀC33T'ꢀ-Bꢀ0Bmꢀ<"%"'ꢀFBꢀ6Bmꢀ<,"#&'ꢀ@Bꢀ.BꢀI#&!#99A!#&ꢀV1#=,!3#"D!J",!3#ꢀ!#ꢀ"ꢀ
<1:A"H3D9=1D"Aꢀ @3D;H9Aqꢀ 8!9A"A=%!="Dꢀ <9DEYlA&"#!J",!3#ꢀ 3Eꢀ -A!:D;ꢀ lA,%3&3#"Dꢀ 43#Y=3L"D9#,ꢀ
[#,9A"=,!3#Gꢀ3#ꢀ"ꢀ<1:A"H3D9=1D"AꢀC33A2!#",!3#ꢀC3H:D9]ꢀ@D",E3AHBꢀ#7ꢀA$7ꢀ560$7ꢀ89:7ꢀDSꢁM'ꢀ34<'ꢀUOPB
ZQS\ꢀ<9:9%A:31A'ꢀ8Bmꢀ<"%"'ꢀFBꢀ6Bmꢀ<,"#&'ꢀ@Bꢀ.BꢀV9^@,ꢀ-W!G,92ꢀ89,9A3H9,"DD!=ꢀa!=;=D!=ꢀ<1:A"H3D9=1D9Gꢀ
L!"ꢀF1D,!=3H:3#9#,ꢀ<9DEYꢁGG9HXD;Bꢀ#7ꢀA$7ꢀ560$7ꢀ89:7ꢀDSꢁL'ꢀ34='ꢀSQQMB
'
ACS Paragon Plus Environment

Page 19 of 19
Journal of the American Chemical Society
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
ACS Paragon Plus Environment